CN109301226A - A kind of preparation process of the lithium ion battery electrode material modified based on graphene - Google Patents
A kind of preparation process of the lithium ion battery electrode material modified based on graphene Download PDFInfo
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- CN109301226A CN109301226A CN201811229277.6A CN201811229277A CN109301226A CN 109301226 A CN109301226 A CN 109301226A CN 201811229277 A CN201811229277 A CN 201811229277A CN 109301226 A CN109301226 A CN 109301226A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 158
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 238000010792 warming Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 150000003378 silver Chemical class 0.000 claims abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- 229910052709 silver Inorganic materials 0.000 claims abstract description 22
- 239000004332 silver Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 238000002444 silanisation Methods 0.000 claims abstract description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000002604 ultrasonography Methods 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 230000003252 repetitive effect Effects 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 38
- 239000004408 titanium dioxide Substances 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 210000003850 cellular structure Anatomy 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910020175 SiOH Inorganic materials 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000010410 dusting Methods 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000012286 potassium permanganate Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 125000005372 silanol group Chemical group 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- -1 modified graphite alkene Chemical class 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229910014913 LixSi Inorganic materials 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation process of lithium ion battery electrode material modified based on graphene, specific preparation process is as follows: preparing graphene oxide；Prepare silanization graphene oxide；The silanization graphene oxide of preparation is added to the water, after being warming up to 40 DEG C of ultrasonic disperse 30min, keeps temperature-resistant, the silver nitrate solution that concentration is 200mg/L is added thereto, then ultrasonic vibration 4h, filtration washing, obtain silver-based graphene oxide；The silver-based graphene oxide of preparation is added to the water and is warming up to 50 DEG C of hydrolysis 30min, is then filtered, the product adding into acetone obtained after filtering, while triphenyl phosphorus being added thereto, 60 DEG C of reaction 3h are warming up to, obtains the modified silver-based graphene oxide in surface.Lithium ion battery negative material prepared by the present invention is not only able to satisfy the requirement of specific capacity, and specific capacity reaches 1123mAh/g, while can use by long-term repetitive cycling, and when being recycled 36-45 times, specific capacity variation less, is maintained at 680mAh/g.
Description
Technical field
The invention belongs to field of lithium ion battery, it is related to a kind of lithium ion battery electrode material modified based on graphene
Preparation process.
Background technique
With the development of portable consumer electronics (mobile phone, video camera, portable computer), field of batteries receives new
Impact, is badly in need of the battery of high-energy density to meet the needs of market.However lead-acid battery is not appropriate for these applications, people's handle
Concern transfers to have invested ickel-cadmium cell, but is finally surmounted in early 1990s by lithium ion battery,
Its specific capacity influences the performance of battery in lithium ion battery use process, while the cycle-index of battery determines electricity
The service life in pond, existing lithium ion battery negative material is usually using grapheme material, but graphene is in use process
In, since during charge and discharge cycles, the insertion and abjection of lithium ion can make carbon structure expand and shrink, the machine of generation
Tool stress can make grapheme material gradually dusting, cause lithium ion irreversible loss, and structure collapses finally fall off from collector
Cycle performance is caused to be decayed rapidly, while the specific capacity of grapheme material is also difficult meet demand.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation process of lithium ion battery electrode material modified based on graphene,
The electrode material is not only able to satisfy the requirement of specific capacity, and specific capacity reaches 1123mAh/g, while can follow by long-term repetition
Ring uses, and when being recycled 36-45 times, specific capacity variation less, is maintained at 680mAh/g.
Electrode material prepared by the present invention is by the surface grafting siloxane branches in graphene oxide, while on branch
Silver ion is adsorbed, and in the effect of catalyst triphenyl phosphorus between the adjacent two-SiOH silanol groups of surface of graphene oxide
Lower generation silanol condensation reaction, formation-Si-O-Si- bridging structure, so that between surface of graphene oxide and-Si-O-Si- key
Cellular structure is formed, so that surface of graphene oxide forms one layer of multi-pore channel structure, when as electrode material, lithium ion is not only
It can be adsorbed on graphene edge, stored in gap on the surface of graphene, while can be filled in the duct of surface formation, lithium
With silication symphysis at the Li of unformed shapexSi, and then the capacity of lithium ion is increased, specific capacity is improved, and after reduction
Graphene surface by the compound layer of titanium dioxide of sedimentation, further increase the specific capacity of electrode, solve existing lithium from
Sub- cell negative electrode material specific capacity lower the problem of cannot meeting the requirements.
The present invention is made by adsorbing silver ion in one layer of multi-pore channel structure on the surface of graphene by the support of silver ion
With so that the cellular structure formed between adjacent silicon oxygen bond is secured, wherein silicon is still able to maintain structure not after repeatedly reacting with lithium
Become, improves its cycle-index, and due to the high conduction performance of silver, and then can be improved the conductive capability of negative electrode material, simultaneously
Titanium dioxide is uniformly compounded in the surface of graphene, is filled in graphene sheet layer gap by titanium dioxide, the graphite of diminution
Alkene lamella gap, but pass through the support fixed function of titanium dioxide, it can effectively realize that graphene is acted on lithium ion
The collapsing that graphene gap is caused during charging and discharging, influences the circulation of electrode material, solves existing lithium ion battery and exist
During charge and discharge cycles, the insertion and abjection of lithium ion can make carbon structure expand and shrink, the mechanical stress meeting of generation
Make grapheme material gradually dusting, causes lithium ion irreversible loss, structure collapses, finally falling off from collector causes to recycle
The problem of performance decays rapidly.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation process of the lithium ion battery electrode material modified based on graphene, specific preparation process are as follows:
The first step prepares graphene oxide using conventional method: a certain amount of graphite powder being added in concentrated sulfuric acid solution, together
When sodium nitrate is added thereto, 10-15min is then reacted in ice-water bath, potassium permanganate is then added thereto, is stirred to react
It is warming up to 50 DEG C of reaction 5-6h after 5-10min, is cooled to room temperature, hydrogen peroxide is then slowly added dropwise, until the color of solution becomes
Until buff, it is then centrifuged for drying, obtains graphene oxide；
The graphene oxide of preparation is added in lower ultrasonic disperse 2h in ethyl alcohol, takes upper layer after then precipitating 12h by second step
Liquid is wherein the less graphene of the number of plies in upper liquid, then carries out ultrasound precipitation again, repeated multiple times, that collects is upper
Layer liquid is added in reaction vessel, is warming up to 70 DEG C, while 3-aminopropyltriethoxysilane being added thereto, back flow reaction 5h
After carry out filtration washing, obtain silanization graphene oxide；Due to containing epoxy group, 3- aminopropyl three in graphene oxide
With epoxy group ring-opening reaction can occur for the amino in Ethoxysilane at 70 DEG C, so that in graphene oxide layer
Epoxidation is unfolded into hydroxyl and secondary amine；Ethyl alcohol 6mL is added in every gram of graphene oxide, 3- ammonia is added in every 10mL upper liquid
Base propyl-triethoxysilicane 0.12-0.13g；
The silanization graphene oxide prepared in second step is added to the water by third step, is warming up to 40 DEG C of ultrasonic disperses
It after 30min, keeps temperature-resistant, the silver nitrate solution that concentration is 200mg/L is added thereto, then ultrasonic vibration 4h, filtering
Washing, obtains silver-based graphene oxide；Due to containing-NH- base in silanization graphene oxide, concussion can be with silver at 40 DEG C
Complexation reaction occurs for ion, so that silver ion is supported on the surface of graphene oxide；Wherein every gram of silanization graphite oxide
Alkene is added in 15-20mL water, and the silver nitrate solution that 20-22mL concentration is 200mg/L is added in every gram of silanization graphene oxide；
The silver-based graphene oxide prepared in third step is added to the water and is warming up to 50 DEG C of hydrolysis 30min, then by the 4th step
It is filtered, the product adding into acetone obtained after filtering, while triphenyl phosphorus being added thereto, be warming up to 60 DEG C of reaction 3h,
Obtain the modified silver-based graphene oxide in surface；Triphenyl phosphorus 0.31-0.32g is wherein added in every Ke Yinji graphene oxide,
Contain-SiOC in middle silver-based graphene oxide2H5, hydrolyzed under certain temperature in water, formation-SiOH, surface of graphene oxide phase
Silanol condensation reaction, formation-Si-O-Si- occurs between two adjacent-SiOH silanol groups under the action of catalyst triphenyl phosphorus
Bridging structure, so that cellular structure is formed between surface of graphene oxide and-Si-O-Si- key, so that surface of graphene oxide shape
At one layer of multi-pore channel structure, as shown in Figure 1, lithium ion can not only be adsorbed on graphene edge when as electrode material, deposit
It stores up in gap on the surface of graphene, while can be filled in the duct of surface formation, lithium and silication symphysis are at unformed shape
LixSi, and then the capacity of lithium ion is increased, specific capacity is improved, existing electrode silicon materials pass through in charge and discharge process
Effect between lithium causes silicon materials dusting to collapse, and then makes the reduction of its circulation ability, and in the material of the application preparation,
Simultaneously because the supporting role of silver ion, so that the cellular structure formed between adjacent silicon oxygen bond is secured, wherein silicon is more with lithium
It is constant that it is still able to maintain structure after secondary response, improves its cycle-index, and due to the high conduction performance of silver, and then can be improved negative
The conductive capability of pole material；
The modified silver-based graphene oxide in the surface prepared in 4th step is added in n,N-Dimethylformamide 5th step,
Then solution after dispersion is added in reaction vessel, hydrazine hydrate is added after being warming up to 100 DEG C thereto by ultrasonic disperse 3h, permanent
Temperature reaction 4h, is then filtered washing drying, obtains the modified silver-based graphene in surface；The modified silver-based graphite oxide in every gram of surface
18-20mLN is added in alkene, and in dinethylformamide, hydrazine hydrate 10mL is added in the modified silver-based graphene oxide in every gram of surface；
6th step prepares titanium colloidal sol: 1. metatitanic acid isopropanol being added in ethyl alcohol, being configured to concentration is 0.3-0.5mol/L's
Metatitanic acid aqueous isopropanol；2. 1. metatitanic acid aqueous isopropanol that step is prepared is added in reaction vessel, it is warming up to 60-70 DEG C backward
The sodium hydroxide solution that concentration is 0.5mol/L is wherein added, stirring hydrolyzes 3h, the pH=12- of solution is controlled in whipping process
13, solid product is obtained, it is stand-by after being washed with deionized；3. 2. solid that step is prepared is dissolved in the second that concentration is 3mol/L
In alkanolamine solution, 5-7h is kept the temperature at 100 DEG C and carries out dispergation, obtains titanium colloidal sol；
The modified silver-based graphene in the surface prepared in 5th step is added in the titanium colloidal sol prepared in the 6th step 7th step,
Be put into autoclave, at 300 DEG C, 10MPa hydro-thermal reaction for 24 hours, be then filtered washing obtain the modified titanium-based in surface/
Silver-based Graphene electrodes material；Titanium colloidal sol 5.6-5.8mL wherein is added in the modified silver-based graphene in every gram of surface；Wherein titanium colloidal sol
At high temperature under high pressure, it is decomposed on the surface of the modified silver-based graphene in surface and generates inorganic titanium dioxide, so that titanium dioxide is uniform
It is compounded in the surface of graphene, is filled in graphene sheet layer gap by titanium dioxide, the graphene sheet layer gap of diminution, but
It is the support fixed function by titanium dioxide, can effectively realizes graphene during acting on charging and discharging with lithium ion
The collapsing for causing graphene gap influences the circulation of electrode material, while the addition of titanium dioxide improves the reversible specific volume of electrode
Amount, while capableing of the electric conductivity of reinforcing material, and electronics is shortened by the effect between titanium dioxide and collector and is passed
Defeated path can help cycle performance and high rate performance that material is improved in the quick insert material of lithium ion.
The electrode material is recycled as the negative electrode material of lithium ion battery.
Beneficial effects of the present invention:
Electrode material prepared by the present invention is not only able to satisfy the requirement of specific capacity, and specific capacity reaches 1123mAh/g, while energy
It is enough used by long-term repetitive cycling, when being recycled 36-45 times, specific capacity variation less, is maintained at 680mAh/g.
Electrode material prepared by the present invention is by the surface grafting siloxane branches in graphene oxide, while on branch
Silver ion is adsorbed, and in the effect of catalyst triphenyl phosphorus between the adjacent two-SiOH silanol groups of surface of graphene oxide
Lower generation silanol condensation reaction, formation-Si-O-Si- bridging structure, so that between surface of graphene oxide and-Si-O-Si- key
Cellular structure is formed, so that surface of graphene oxide forms one layer of multi-pore channel structure, when as electrode material, lithium ion is not only
It can be adsorbed on graphene edge, stored in gap on the surface of graphene, while can be filled in the duct of surface formation, lithium
With silication symphysis at the Li of unformed shapexSi, and then the capacity of lithium ion is increased, specific capacity is improved, and after reduction
Graphene surface by the compound layer of titanium dioxide of sedimentation, further increase the specific capacity of electrode, solve existing lithium from
Sub- cell negative electrode material specific capacity lower the problem of cannot meeting the requirements.
The present invention is made by adsorbing silver ion in one layer of multi-pore channel structure on the surface of graphene by the support of silver ion
With so that the cellular structure formed between adjacent silicon oxygen bond is secured, wherein silicon is still able to maintain structure not after repeatedly reacting with lithium
Become, improves its cycle-index, and due to the high conduction performance of silver, and then can be improved the conductive capability of negative electrode material, simultaneously
Titanium dioxide is uniformly compounded in the surface of graphene, is filled in graphene sheet layer gap by titanium dioxide, the graphite of diminution
Alkene lamella gap, but pass through the support fixed function of titanium dioxide, it can effectively realize that graphene is acted on lithium ion
The collapsing that graphene gap is caused during charging and discharging, influences the circulation of electrode material, solves existing lithium ion battery and exist
During charge and discharge cycles, the insertion and abjection of lithium ion can make carbon structure expand and shrink, the mechanical stress meeting of generation
Make grapheme material gradually dusting, causes lithium ion irreversible loss, structure collapses, finally falling off from collector causes to recycle
The problem of performance decays rapidly.
Detailed description of the invention
In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the drawings.
Fig. 1 is the modified silver-based graphite oxide alkene reaction schematic diagram in surface of the present invention；
Fig. 2, which passes through for the electrode material of embodiment 2-7 preparation as the negative electrode material of lithium ion battery, to be recycled for multiple times
Specific discharge capacity measurement result afterwards.
Specific embodiment
Fig. 1 and Fig. 2 are please referred to, is described in detail in conjunction with following examples:
Embodiment 1:
Titanium colloidal sol is prepared, specific preparation process is as follows:
1. metatitanic acid isopropanol is added in ethyl alcohol, it is configured to the metatitanic acid aqueous isopropanol that concentration is 0.3-0.5mol/L；
2. 1. metatitanic acid aqueous isopropanol that step is prepared is added in reaction vessel, add thereto after being warming up to 60-70 DEG C
Enter the sodium hydroxide solution that concentration is 0.5mol/L, stirring hydrolyzes 3h, the pH=12-13 of solution is controlled in whipping process, is obtained
Solid product, it is stand-by after being washed with deionized；
3. 2. solid that step is prepared is dissolved in the ethanolamine solutions that concentration is 3mol/L, 5-7h is kept the temperature at 100 DEG C
Dispergation is carried out, titanium colloidal sol is obtained；
Embodiment 2:
A kind of preparation process of the lithium ion battery electrode material modified based on graphene, specific preparation process are as follows:
The first step prepares graphene oxide using conventional method: a certain amount of graphite powder being added in concentrated sulfuric acid solution, together
When sodium nitrate is added thereto, 10-15min is then reacted in ice-water bath, potassium permanganate is then added thereto, is stirred to react
It is warming up to 50 DEG C of reaction 5-6h after 5-10min, is cooled to room temperature, hydrogen peroxide is then slowly added dropwise, until the color of solution becomes
Until buff, it is then centrifuged for drying, obtains graphene oxide；
The graphene oxide of 100g preparation is added in 0.6L ethyl alcohol in lower ultrasonic disperse 2h, then precipitates 12h by second step
After take upper liquid, be wherein the less graphene of the number of plies in upper liquid, then carry out ultrasound precipitation again, it is repeated multiple times, collect
Obtained 100mL upper liquid is added in reaction vessel, is warming up to 70 DEG C, while three ethoxy of 1.2g3- aminopropyl being added thereto
Base silane carries out filtration washing after back flow reaction 5h, obtains silanization graphene oxide；
The silanization graphene oxide prepared in 100g second step is added in 1.5L water third step, is warming up to 40 DEG C and surpasses
It after sound disperses 30min, keeps temperature-resistant, the silver nitrate solution that 2L concentration is 200mg/L is added thereto, then ultrasonic vibration
4h, filtration washing obtain silver-based graphene oxide；
The silver-based graphene oxide prepared in 100g third step is added to the water and is warming up to 50 DEG C of hydrolysis 30min by the 4th step,
Then it is filtered, the product adding into acetone obtained after filtering, while 31g triphenyl phosphorus being added thereto, be warming up to 60 DEG C
3h is reacted, the modified silver-based graphene oxide in surface is obtained；
1.8LN, N- dimethyl methyl is added in the modified silver-based graphene oxide in the surface prepared in the 4th step of 100g by the 5th step
In amide, then the solution after dispersion is added in reaction vessel, 1L is added thereto after being warming up to 100 DEG C by ultrasonic disperse 3h
Then hydrazine hydrate, isothermal reaction 4h are filtered washing drying, obtain the modified silver-based graphene in surface；
Titanium prepared by 0.56L embodiment 1 is added in the modified silver-based graphene in the surface prepared in the 5th step of 100g by the 6th step
It in colloidal sol, is put into autoclave, hydro-thermal reaction for 24 hours, is then filtered and washs to change to surface at 300 DEG C, 10MPa
Property titanium-based/silver-based Graphene electrodes material.
Embodiment 3:
A kind of preparation process of the lithium ion battery electrode material modified based on graphene, specific preparation process are as follows:
The first step prepares graphene oxide using conventional method: a certain amount of graphite powder being added in concentrated sulfuric acid solution, together
When sodium nitrate is added thereto, 10-15min is then reacted in ice-water bath, potassium permanganate is then added thereto, is stirred to react
It is warming up to 50 DEG C of reaction 5-6h after 5-10min, is cooled to room temperature, hydrogen peroxide is then slowly added dropwise, until the color of solution becomes
Until buff, it is then centrifuged for drying, obtains graphene oxide；
The graphene oxide of 100g preparation is added in 0.6L ethyl alcohol in lower ultrasonic disperse 2h, then precipitates 12h by second step
After take upper liquid, be wherein the less graphene of the number of plies in upper liquid, then carry out ultrasound precipitation again, it is repeated multiple times, collect
Obtained 100mL upper liquid is added in reaction vessel, is warming up to 70 DEG C, while three ethoxy of 1.3g3- aminopropyl being added thereto
Base silane carries out filtration washing after back flow reaction 5h, obtains silanization graphene oxide；
The silanization graphene oxide prepared in 100g second step is added in 2L water, is warming up to 40 DEG C of ultrasounds by third step
It after dispersing 30min, keeps temperature-resistant, the silver nitrate solution that 2.2L concentration is 200mg/L is added thereto, then ultrasonic vibration
4h, filtration washing obtain silver-based graphene oxide；
The silver-based graphene oxide prepared in 100g third step is added to the water and is warming up to 50 DEG C of hydrolysis 30min by the 4th step,
Then it is filtered, the product adding into acetone obtained after filtering, while 32g triphenyl phosphorus being added thereto, be warming up to 60 DEG C
3h is reacted, the modified silver-based graphene oxide in surface is obtained；
2LN, N- dimethyl formyl is added in the modified silver-based graphene oxide in the surface prepared in the 4th step of 100g by the 5th step
In amine, then the solution after dispersion is added in reaction vessel, is warming up to after 100 DEG C and 1L water is added thereto by ultrasonic disperse 3h
Hydrazine is closed, then isothermal reaction 4h is filtered washing drying, obtain the modified silver-based graphene in surface；
Titanium prepared by 0.58L embodiment 1 is added in the modified silver-based graphene in the surface prepared in the 5th step of 100g by the 6th step
It in colloidal sol, is put into autoclave, hydro-thermal reaction for 24 hours, is then filtered and washs to change to surface at 300 DEG C, 10MPa
Property titanium-based/silver-based Graphene electrodes material.
Embodiment 4:
Preparation process is same as Example 2, and the additional amount for the silver nitrate solution that concentration in embodiment 2 is 200mg/L is changed
For 1L.
Embodiment 5:
A kind of preparation process of the lithium ion battery electrode material modified based on graphene, specific preparation process are as follows:
The first step prepares graphene oxide using conventional method；
The graphene oxide of 100g preparation is added in 0.6L ethyl alcohol in lower ultrasonic disperse 2h, then precipitates 12h by second step
After take upper liquid, be wherein the less graphene of the number of plies in upper liquid, then carry out ultrasound precipitation again, it is repeated multiple times, collect
Obtained 100mL upper liquid is added in reaction vessel, is warming up to 70 DEG C, while three ethoxy of 1.3g3- aminopropyl being added thereto
Base silane carries out filtration washing after back flow reaction 5h, obtains silanization graphene oxide；
The silanization graphene oxide prepared in 100g second step is added to the water and is warming up to 50 DEG C of hydrolysis by third step
Then 30min is filtered, the product adding into acetone obtained after filtering, while 32g triphenyl phosphorus being added thereto, heating
To 60 DEG C of reaction 3h, surface modified graphene oxide is obtained；
2LN, dinethylformamide is added in the surface modified graphene oxide prepared in 100g third step by the 4th step
In, then ultrasonic disperse 3h the solution after dispersion is added in reaction vessel, be warming up to after 100 DEG C and 1L hydration is added thereto
Then hydrazine, isothermal reaction 4h are filtered washing drying, obtain surface modified graphite alkene；
5th step, titanium colloidal sol prepared by the surface modified graphite alkene prepared in the 4th step of 100g addition 0.58L embodiment 1
In, it is put into autoclave, hydro-thermal reaction for 24 hours, is then filtered washing and obtains surface Modified Titanium at 300 DEG C, 10MPa
Base graphene electrode material.
Embodiment 6:
A kind of preparation process of the lithium ion battery electrode material modified based on graphene, specific preparation process are as follows:
The first step prepares graphene oxide using conventional method；
2LN is added in the graphene oxide prepared in the 100g first step by second step, in dinethylformamide, ultrasound point
3h is dissipated, then the solution after dispersion is added in reaction vessel, is warming up to after 100 DEG C and 1L hydrazine hydrate is added thereto, constant temperature is anti-
4h is answered, washing drying is then filtered, obtains modified graphene；
Third step the modified graphene prepared in 100g second step is added in titanium colloidal sol prepared by 0.58L embodiment 1,
It is put into autoclave, hydro-thermal reaction for 24 hours, is then filtered washing and obtains Modified Titanium base graphite at 300 DEG C, 10MPa
Alkene electrode material.
Embodiment 7:
A kind of preparation process of the lithium ion battery electrode material modified based on graphene, specific preparation process are as follows:
The first step prepares graphene oxide using conventional method: a certain amount of graphite powder being added in concentrated sulfuric acid solution, together
When sodium nitrate is added thereto, 10-15min is then reacted in ice-water bath, potassium permanganate is then added thereto, is stirred to react
It is warming up to 50 DEG C of reaction 5-6h after 5-10min, is cooled to room temperature, hydrogen peroxide is then slowly added dropwise, until the color of solution becomes
Until buff, it is then centrifuged for drying, obtains graphene oxide；
The graphene oxide of 100g preparation is added in 0.6L ethyl alcohol in lower ultrasonic disperse 2h, then precipitates 12h by second step
After take upper liquid, be wherein the less graphene of the number of plies in upper liquid, then carry out ultrasound precipitation again, it is repeated multiple times, collect
Obtained 100mL upper liquid is added in reaction vessel, is warming up to 70 DEG C, while three ethoxy of 1.2g3- aminopropyl being added thereto
Base silane carries out filtration washing after back flow reaction 5h, obtains silanization graphene oxide；
The silanization graphene oxide prepared in 100g second step is added in 1.5L water third step, is warming up to 40 DEG C and surpasses
It after sound disperses 30min, keeps temperature-resistant, the silver nitrate solution that 2L concentration is 200mg/L is added thereto, then ultrasonic vibration
4h, filtration washing obtain silver-based graphene oxide；
The silver-based graphene oxide prepared in 100g third step is added to the water and is warming up to 50 DEG C of hydrolysis 30min by the 4th step,
Then it is filtered, the product adding into acetone obtained after filtering, while 31g triphenyl phosphorus being added thereto, be warming up to 60 DEG C
3h is reacted, the modified silver-based graphene oxide in surface is obtained；
1.8LN, N- dimethyl methyl is added in the modified silver-based graphene oxide in the surface prepared in the 4th step of 100g by the 5th step
In amide, then the solution after dispersion is added in reaction vessel, 1L is added thereto after being warming up to 100 DEG C by ultrasonic disperse 3h
Then hydrazine hydrate, isothermal reaction 4h are filtered washing drying, obtain the modified silver-based graphene in surface.
Embodiment 8:
Using electrode material prepared by embodiment 2-7 as the negative electrode material of lithium ion battery by being recycled for multiple times, point
The specific discharge capacity after different numbers Ce Ding not be recycled, as a result as shown in Figure 2:
Cellular structure is formed between surface of graphene oxide and-Si-O-Si- key first, so that surface of graphene oxide shape
At one layer of multi-pore channel structure, when as electrode material, lithium ion can not only be adsorbed on graphene edge, be stored in graphene
It in surface void, while can be filled in the duct of surface formation, lithium is with silication symphysis at the Li of unformed shapexSi, in turn
The capacity for increasing lithium ion, improves specific capacity, at the same silver ion addition simultaneously because silver ion supporting role so that
The cellular structure formed between adjacent silicon oxygen bond is secured, and wherein it is constant to be still able to maintain structure after repeatedly reacting with lithium for silicon, improves
Its cycle-index, and due to the high conduction performance of silver, and then can be improved the conductive capability of negative electrode material；As silver ion contains
The reduction of amount, duct supporting role reduces, so that causing duct to collapse in negative electrode material cyclic process, discharges under specific volume
Reduction of speed rate improves；
Secondly, titanium colloidal sol is at high temperature under high pressure, on surface, the surface of modified silver-based graphene, which is decomposed, generates inorganic titanium dioxide
Titanium is filled in graphene sheet layer gap so that titanium dioxide is uniformly compounded in the surface of graphene by titanium dioxide, is reduced
Graphene sheet layer gap, but by the support fixed function of titanium dioxide, can effectively realize graphene with lithium from
Cause the collapsing in graphene gap during son effect charging and discharging, influence the circulation of electrode material, at the same titanium dioxide plus
Enter to improve the electric discharge specific volume of electrode, while capableing of the electric conductivity of reinforcing material, and by between titanium dioxide and collector
Effect shorten electron-transport path, can help to improve the cycle performance of material in the quick insert material of lithium ion
And high rate performance.
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to better explain the present invention
Principle and practical application, so that skilled artisan be enable to better understand and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (8)
1. a kind of preparation process of the lithium ion battery electrode material modified based on graphene, which is characterized in that specifically prepared
Journey is as follows:
The first step prepares graphene oxide；
The graphene oxide of preparation is added in lower ultrasonic disperse 2h in ethyl alcohol, takes upper liquid after then precipitating 12h by second step,
It is wherein the less graphene of the number of plies in upper liquid, then carries out ultrasound precipitation again, repeated multiple times, the upper liquid collected
It is added in reaction vessel, is warming up to 70 DEG C, while 3-aminopropyltriethoxysilane being added thereto, back flow reaction 5h is laggard
Row filtration washing obtains silanization graphene oxide；
The silanization graphene oxide prepared in second step is added to the water by third step, is warming up to 40 DEG C of ultrasonic disperse 30min
Afterwards, it keeps temperature-resistant, the silver nitrate solution that concentration is 200mg/L is added thereto, then ultrasonic vibration 4h, filtration washing,
Obtain silver-based graphene oxide；
The silver-based graphene oxide prepared in third step is added to the water and is warming up to 50 DEG C of hydrolysis 30min, then carries out by the 4th step
Filtering, the product adding into acetone obtained after filtering, while triphenyl phosphorus being added thereto, 60 DEG C of reaction 3h are warming up to, are obtained
Surface is modified silver-based graphene oxide；
5th step the modified silver-based graphene oxide in the surface prepared in the 4th step is added in n,N-Dimethylformamide, ultrasound
Disperse 3h, then the solution after dispersion is added in reaction vessel, hydrazine hydrate is added after being warming up to 100 DEG C thereto, constant temperature is anti-
4h is answered, washing drying is then filtered, obtains the modified silver-based graphene in surface；
6th step prepares titanium colloidal sol using alkali precipitation Hydrolyze method；
The modified silver-based graphene in the surface prepared in 5th step is added in the titanium colloidal sol prepared in the 6th step, is put by the 7th step
In autoclave, hydro-thermal reaction for 24 hours, is then filtered washing and obtains the modified titanium-based/silver-based in surface at 300 DEG C, 10MPa
Graphene electrodes material.
2. a kind of preparation process of lithium ion battery electrode material modified based on graphene according to claim 1,
It is characterized in that, ethyl alcohol 6mL is added in second step in every gram of graphene oxide, three second of 3- aminopropyl is added in every 10mL upper liquid
Oxysilane 0.12-0.13g.
3. a kind of preparation process of lithium ion battery electrode material modified based on graphene according to claim 1,
It is characterized in that, every gram of silanization graphene oxide is added in 15-20mL water in third step, adds in every gram of silanization graphene oxide
Enter the silver nitrate solution that 20-22mL concentration is 200mg/L.
4. a kind of preparation process of lithium ion battery electrode material modified based on graphene according to claim 1,
It is characterized in that, triphenyl phosphorus 0.31-0.32g is added in the 4th step in every Ke Yinji graphene oxide.
5. a kind of preparation process of lithium ion battery electrode material modified based on graphene according to claim 1,
It is characterized in that, the modified silver-based graphene oxide addition 18-20mLN in every gram of surface in the 5th step, in dinethylformamide, every gram
Hydrazine hydrate 10mL is added in the modified silver-based graphene oxide in surface.
6. a kind of preparation process of lithium ion battery electrode material modified based on graphene according to claim 1,
It is characterized in that, the specific preparation process of titanium colloidal sol is as follows in the 6th step:
1. metatitanic acid isopropanol is added in ethyl alcohol, it is configured to the metatitanic acid aqueous isopropanol that concentration is 0.3-0.5mol/L；
2. 1. metatitanic acid aqueous isopropanol that step is prepared is added in reaction vessel, it is added thereto after being warming up to 60-70 DEG C dense
Degree is the sodium hydroxide solution of 0.5mol/L, and stirring hydrolyzes 3h, the pH=12-13 of solution is controlled in whipping process, obtains solid
Product, it is stand-by after being washed with deionized；
3. 2. solid that step is prepared is dissolved in the ethanolamine solutions that concentration is 3mol/L, 5-7h is kept the temperature at 100 DEG C and is carried out
Dispergation obtains titanium colloidal sol.
7. a kind of preparation process of lithium ion battery electrode material modified based on graphene according to claim 1,
It is characterized in that, titanium colloidal sol 5.6-5.8mL is added in the modified silver-based graphene in every gram of surface in the 7th step.
8. a kind of preparation process of lithium ion battery electrode material modified based on graphene according to claim 1,
It is characterized in that, which uses as the negative electrode material of lithium ion battery.
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