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WO1998038685A2 - Utilisation de noir de carbone comme materiau anodique pour accumulateurs aux ions de lithium - Google Patents

Utilisation de noir de carbone comme materiau anodique pour accumulateurs aux ions de lithium Download PDF

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Publication number
WO1998038685A2
WO1998038685A2 PCT/US1998/003408 US9803408W WO9838685A2 WO 1998038685 A2 WO1998038685 A2 WO 1998038685A2 US 9803408 W US9803408 W US 9803408W WO 9838685 A2 WO9838685 A2 WO 9838685A2
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Prior art keywords
carbon
anode
cell
carbon black
lithium
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PCT/US1998/003408
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English (en)
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WO1998038685A9 (fr
WO1998038685A3 (fr
Inventor
Eric Burton Sebok
Charles Ray Herd
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Columbian Chemicals Company
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Priority to AU65359/98A priority Critical patent/AU6535998A/en
Publication of WO1998038685A2 publication Critical patent/WO1998038685A2/fr
Publication of WO1998038685A3 publication Critical patent/WO1998038685A3/fr
Publication of WO1998038685A9 publication Critical patent/WO1998038685A9/fr

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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
    • H01M4/58—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
    • 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
    • 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
    • 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

Definitions

  • the apparatus of the present invention relates to improved lithium-ion batteries. More particularly, the present invention relates to improved electrodes in lithium-ion batteries, the improved electrodes containing specific carbon blacks.
  • lithium-ion batteries are well known in the art and generally comprise features such as those described in U.S. Patent No. 5,571,638 (Satoh et al, Uthium Secondary Battery) which is hereby incorporated by reference in its entirety.
  • Uthium-ion (U-ion) batteries are a relatively new type of secondary
  • U-ion cells are typically composed of three major components: cathode, anode, and electrolyte.
  • the cathode is generally comprised of a Uthium-Metal- Oxide (e.g. UCo0 2 ), while the anode mostly contains a carbon material capable of intercalation and release of lithium ions from and to the cathode (during the charge and discharge cycles, respectively).
  • the carbon material used in the anode must have a low surface area, high cycling capacity, and excellent stability over extended cycling.
  • the electrolyte serves as a conductive medium through which lithium ions can be transported to and from the electrodes. In the past, electrolytes have mainly been liquid in nature; however, new solid polymer electrolytes are also now being used for U-ion batteries.
  • the present invention primarily focuses on the anode, more specifically the use of a certain carbon material as the chief anode material.
  • This new anode material is a unique form of carbon black known as thermal black.
  • This type of carbon black is unlike any other form of carbon black mentioned for use in U-ion batteries in the prior art as it has a mean particle size greater than 100 nm (typically -400 nm) and is produced by the thermal process described herein (as opposed to the furnace or acetylene process).
  • the use of this type of carbon black in U-ion battery anodes is also unique in that it is used in the anode for intercalation of lithium ions from the cathode, and can comprise nearly 100% of the anode. Previous inventions primarily disclose the use of carbon black in smaller percentages for conductivity purposes only.
  • Binder et al. in U.S. Patent 4,543,305 claim the use of low (60 m 2 /g) and high (1500 m 2 /g) surface area carbon blacks in cathodes of primary cells which are bonded with Teflon (5 to 10%) on a nickel support.
  • the main claim of this work is that washing of the carbon blacks with acetone increases the operating voltage and cell life.
  • higher surface area carbon blacks >60 m 2 /g
  • Fauteux et al. also specify the use of only 10 to 50 parts by weight of the carbon black in the anode which is significantly lower than the > 85 wt% level specified in the present invention.
  • U.S. Patent No. 5,426,006 by Delnick et al. also teaches the use of disordered carbons in anodes of rechargeable lithium ion batteries; however, these carbons are prepared from carbonization of "polymeric high internal phase emulsions" which in no way is comparable to carbon black in either its morphology or microstructure.
  • the disordered material should have an average interlayer spacing (d n02 ) between the carbon planes of >3.7 A, which is larger than the d 002 of the carbon blacks specified in the present invention (d 002 ranges from 3.390 to 3.565 A).
  • Mitate et al. in U.S. Patent No. 5,478,364 teach the use of copper oxide coated graphite in the anodes of lithium secondary batteries for higher charge/discharge capacity. They teach in this patent that the use of disordered carbons is actually unfavorable and that the graphite : copper ratio should fall in the approximate range of 98 : 2 to 60 : 40. This configuration is much different than that specified in the present invention where a carbon black with moderate disorder and in a concentration of > 85wt% is specified for the anode. Mitate et al. also specify the use of a conductive material at an approximately 50 wt% concentration in the cathode for conductive purposes only.
  • thermal carbon black in the anode at a concentration of > 85 wt% for intercalation of Kthium ions.
  • the Mitate et al. patent describes the use of thermal black in the cathode for conductive purposes only and not for intercalation.
  • U.S. Patent No. 5,028,500 by Fong et al. describes the use of a carbonaceous anode (or first electrode as they define it) for rechargeable lithium ion batteries.
  • g is the degree of graphitization and ranges between 0 and 1.
  • the mean g for a two phase carbonaceous composition should be about 0.4 with one phase having a g of >0.8 (i.e. highly graphitic).
  • This carbonaceous composition is composed of a mixture of finely milled graphite (g about 1.0) and a pitch binder which is then heated to convert the pitch to coke or a partially graphitized type of carbon (this material is referred to as isotropic graphite and preferably this material has a g above about 0.4 and is stated as being commercially available from Graphite Sales, Inc. of Chagrin Falls, Ohio, USA).
  • Another material described as meeting the above criteria is spherical graphite that is also commercially available from Graphite Co, of Chicago, Illinois, USA.
  • the degree of graphitization for anode carbons "A" and “B” described in the present invention have g values ⁇ 0 which indicates that these carbons are significantly more disordered than that considered appropriate in the Fong et al. patent. That is, it has been implicitly assumed by Fong et al. that any carbons used in the anodes would have d 002 values less than 3.450 A and greater than 3.365 A since it is clearly stated that the graphitization parameter, g, ranges from 0 to 1. As noted above, anode carbons "A” and “B” of the present invention have g values outside the range of 0 to 1. The inventors in U.S. Patent No.
  • 5,028,500 also state that 1 to 12 wt% of a filamentous carbon black is used in the anode to reduce capacity fade during cycling of the battery and to prevent the need for applying pressure to the cell (this prevents dendritic growth of lithium metal between the anode and cathode).
  • the filamentous carbon black is only specified by its surface area which is listed as being less than 50 m 2 /g and preferably 40 m 2 /g. These values are significantly higher than that for the carbon blacks described in the present invention.
  • U.S. Patent No. 5,510,209 issued to Abraham et al. describes a lithium/oxygen battery where the anode is lithium metal and the cathode is oxygen gas taken from the air.
  • a carbonaceous powder is mixed with a polymer electrolyte to serve as a porous medium in which the oxygen is reduced to form U 2 0.
  • the patent teaches the use of high surface area carbons such as acetylene blacks (about 40 m 2 /g surface area) at a 20 to 40 wt% level in a polymer electrolyte.
  • cathode composition would be suitable with already lithiated graphitic carbons such as graphite, petroleum coke, benzene or other carbonaceous materials.
  • acetylene black as mentioned previously, is different from the anode carbons described in the present invention, and the other carbonaceous materials are not described in detail, but would be expected to be different from those described in the present invention.
  • the carbon blacks are preferentially heat treated in the range of 1500 to 3000 °C and preferably between 2500 and 3000 °C to provide a higher degree of graphitic order, and, in fact, it is taught that the use of carbon blacks subjected to no heat treatment is unfavorable.
  • the specified anode carbon blacks are all larger in primary particle size, lower in surface area, and more disordered with d 002 values >3.46 A (for anode carbon blacks "A" and "B" only) than the specified carbon blacks in the Satoh et al. patent. Also, the Satoh et al.
  • Binder et al. describes in U.S. Patent No. 5,601,948, the plasma treatment of a porous carbon black cathode in a primary battery (lithium and other metals can function as anodes).
  • the carbon black is specified as Shawinigan (an acetylene black) and it is used at a 90% loading (weight or volume not specified) with 10% Teflon® used as binder.
  • the application and type of carbon black are different than that described for the carbon black in the present invention.
  • Dasgupta et al. describes a lithium-manganese oxide electrode (cathode) for a rechargeable lithium battery in U.S. Patent No. 5,601,952. They describe the use of up to 6vol% of a fine carbon compound in the cathode for conductive purposes only.
  • the carbon compound is listed as being acetylene black, petroleum coke, or a similar high purity carbon. The application and description of the carbonaceous materials are different than that described for the carbon blacks in the present invention.
  • Yazami et al. in U.S. Patent No. 5,605,772 describes the use of prelithiated raw coke or semi-coke in an anode for a rechargeable lithium ion battery. Additionally the anode contains an ionically conductive polymer and carbon black for conductive purposes.
  • a typical anode was stated as consisting of approximately 60% raw coke, 30% coating polymer and 10% carbon black. The advantage of this anode was that it produced significantly higher reversible capacities of about 1000 rnAh/g.
  • the primary carbonaceous materials used for intercalation in this anode are the cokes and not the carbon black.
  • the carbon black used in this anode at a 10% loading is used only for conductive purposes and its properties are not specified.
  • thermal carbon black is the primary carbonaceous material used in the anode for intercalation at a >85wt% loading.
  • Kaschmitter et al. in U.S. Patent No. 5,636,437, describes a general methodology of preparing electrodes from carbonaceous powders. Electrodes prepared with low surface area ( ⁇ 50 m 2 /g) cokes and graphites were described as being useful for anodes in secondary lithium ion batteries. The specifications of these materials were not clearly defined, but they are certainly different materials compared to the carbon blacks described in the present invention.
  • the lithium-ion batteries of the present invention comprise a cathode, an anode containing or comprising a specific carbon black, an electrolyte and a separator.
  • the present invention relates to a rechargeable battery comprising a cathode, an anode comprising carbon black, an electrolyte, and a separator.
  • the size of the carbon black particles of the anode can be greater than about lOOnm and/or range in particle size between about lOOnm and about 800nm. Further, the carbon black can have an average surface area of less than about 20 m 2 /g.
  • the carbon black particles may be produced by a thermal process.
  • the anode may comprise approximately 85-95% thermal carbon black about 0-10% conductive black and about 5% binder.
  • the separator may comprise polypropylene saturated with 1 molar U PF 6 ethylene carbonate (ECVdimethyl carbonate (DMC) 1:1 (U/U) electrolyte.
  • the electrolyte may comprise an organic solvent and a salt of an alkali metal.
  • the cathode of the rechargeable battery may comprise, for example, lithium metal, alkali metal or a lithium metal oxide.
  • the cathode may also contain up to 10% conductive black and 5% of a binder such as PVDF (polyvinylidene difluoride).
  • cathode and anode may each be capable of reversibly incorporating an alkali metal.
  • the battery cell of the present invention might comprise a rechargeable battery having an alkali metal cathode, an anode comprising a thermal carbon black having an average particle size of greater than about 100 nm, an electrolyte and a separator positioned between the cathode, which may be lithium, and the anode.
  • the rechargeable battery of the present invention may also comprise a cathode of lithium metal oxide and an anode comprising a carbon black produced from a thermal process and having an average carbon black particle size of greater than about 1 OOnm.
  • the present invention might also include a lithium secondary battery comprising a cathode of a lithium metal oxide, an electrolyte, and an improved anode comprising at least about 85% thermal carbon black material of an average particle size of between about lOOnm and about 800 nm, and having a surface area of less than about 20 m 2 /g.
  • the present invention may relate to an improved rechargeable battery of the type having an anode, a lithium cathode, and an electrolyte, an improvement comprising the anode being formed in part of thermal carbon black of an average particle size of greater than about 100 nm. Additionally, the present invention may relate to an improved anode for a rechargeable lithium metal oxide battery, the improved anode comprising a thermal carbon black material having an average particle size of > lOOnm.
  • the present invention relates to lithium-ion batteries comprising anodes containing carbon blacks having the properties described in Table 1 herein.
  • FIG. 1 Cycle life curves for three different cells (laOl, la 17, la22) made with Carbon A.
  • Figure 2 Illustrates the cycle life curve for cell lal 7 made with Carbon A.
  • Figure 3 Illustrates the cycle life curve for cell la22 made with Carbon A.
  • Figure 4 Illustrates voltage curves for three different cells (laO 1 , lal 7, la22) made with Carbon A.
  • Figure 5 Illustrates dQ/dV vs. cell voltage curves for cell laO 1 made with Carbon A.
  • Figure 6 Illustrates dQ/dV vs. cell voltage curves for cell la22 made with Carbon A.
  • Figure 7 Illustrates cycle #20 voltage curve for cell laO 1 made with Carbon
  • Figure 8 Illustrates cycle #20 dQ/dV vs. cell voltage curve for laO 1 made with Carbon A.
  • Figure 9 Illustrates cycle #46 voltage curve for la22 made with Carbon A.
  • Figure 10 Illustrates a signature curve for cell la21 made with Carbon A at cycles 3, 9, and 15.
  • Figure 11 Illustrates a signature curve for cell la22 made with Carbon A at cycles 3, 9, and 15.
  • Figure 12 Illustrates cycle life curves for two different cells (ulOl and ul05) made with MCMB carbon.
  • Figure 13 Illustrates dQ/dV vs. cell voltage for cell ulO 1 made with MCMB carbon.
  • Figure 14 Illustrates cycle life curves for cells ulOl and ul05 made with
  • FIG. 15 Illustrates cycle life curves for cells la03 & la04 made with Carbon
  • Figure 16 Illustrates the voltage curve for cell la03 & la04 made with anode carbon B.
  • Figure 17 Illustrates the cycle 25 voltage curve for cell la04 made with
  • Figure 18 Illustrates the dQ/dV vs. cell voltage for cell la04 made with
  • Figure 19 Illustrates signature curves for cell la23 made with Carbon B.
  • Figure 20 Illustrates signature curves for cell la24 made with Carbon B.
  • Figure 21 Illustrates a cycle life curve for petroleum coke.
  • Figure 22 Illustrates voltage curves for petroleum coke.
  • Figure 23 Illustrates dQ/dV vs. cell voltage curves for petroleum coke.
  • Figure 24 Illustrates cycle life curves for three different cells (la06, la 15, la 19) made with Carbon C.
  • Figure 25 Illustrates a cycle life curve for cell lal 5 made with Carbon C.
  • Figure 26 Illustrates a cycle life curve for cell la06 made with Carbon C.
  • Figure 27 Illustrates a cycle life curve for cell la 19 made with Carbon C.
  • Figure 28 Illustrates voltage curve for three different cells (la06, lal 5, la 19) made with Carbon C.
  • Figure 29 Illustrates dQ/dV vs. cell voltage for two different cells made with
  • Figure 30 Illustrates dQ/dV vs. cell voltage for two different cells made with
  • Figure 31 Illustrates voltage curves for cell la 19 made with Carbon C.
  • Figure 32 Illustrates signature curves for cell la25 made with Carbon C.
  • Figure 33 Illustrates signature curves for cell la26 made with Carbon C.
  • Figure 34 Illustrates cycle life curves for cell la31 made with Carbon A.
  • Figure 35 Illustrates cycle life curves for cell la32 made with Carbon A.
  • Figure 36 Illustrates cycle life curves for cell la33 made with Carbon A.
  • Figure 37 Illustrates cycle life curves for cell la30 made with MCMB carbon.
  • Figure 38 Compares cycle life data for cell la31 made with Carbon A and cell la30 made with MCMB carbon.
  • Figure 39 Illustrates voltage curves for cell la31 made with Carbon A.
  • Figure 40 Illustrates voltage curves for cell la32 made with Carbon A.
  • Figure 41 Illustrates voltage curves for cell la30 made with MCMB carbon.
  • Figure 42 Illustrates signature curve data for cell ls31 made with Carbon A.
  • Figure 43 Illustrates signature curve data for cell ls30 made with MCMB carbon
  • Figure 44 Illustrates cycle life curves for cell la34 made with Carbon C.
  • Figure 45 Illustrates cycle life curves for cell la35 made with Carbon C.
  • Figure 46 Illustrates cycle life curves for cell la36 made with MCMB Carbon.
  • Figure 47 Illustrates cycle life curves for cell la37 made with MCMB Carbon.
  • Figure 48 Compares discharge cycle life of cell la34 made with Carbon C and cell la37 made with MCMB carbon.
  • Figure 49 Illustrates voltage curves for cell la34 made with Carbon C.
  • Figure 50 Illustrates voltage curves for cell la37 made with MCMB carbon. Ust of Tables
  • Table 1 Illustrates various properties of Carbons A, B, and C.
  • Table 2 Illustrates capacity and first cycle efficiency data for three different cells (laO 1, lal 7, la22) made with Carbon A vs. one made with MCMB - all vs. U-metal cathode.
  • Table 3 Illustrates capacity and first cycle efficiency data for two different cells (la03, la04) made with Carbon B vs. one made with petroleum coke - all vs. U-metal cathode.
  • Table 4 Illustrates capacity and first cycle efficiency data for three different cells (la06, lal5, lal9) made with Carbon C vs. one made with MCMB - all vs. U-metal cathode.
  • Table 5 Illustrates capacity and first cycle efficiency data for three different cells (la31 , la32, la33) made with Carbon A vs. one made with MCMB (la30) - all vs. li-metal-Oxide cathode.
  • Table 6 Illustrates capacity and first cycle efficiency data for cell la34 made with Carbon C vs. one made with MCMB (la36) - both vs. U- metal-Oxide cathode.
  • Carbons A B, and C were made as follows and have the properties summarized in TABLE 1. Sample Carbon A was produced using a conventional thermal black process. This process is described in detail in the following reference:
  • Carbon B and Carbon C are heat treated versions of Carbon A.
  • Carbon B was treated at 1500°C, while Carbon C was treated at 2800 °C.
  • Heat treatments were carried out in an inert atmosphere in high temperature furnaces (treatment performed by UCAR Carbon, Parma OH). In each case, the furnace was ramped to the desired temperature as quickly as possible, and held at that temperature for 30 minutes. Heating was then stopped, and the sample was allowed to cool in the inert atmosphere.
  • the test carbons were fabricated into electrodes in the following general way.
  • the test carbon powder was dry mixed with ca. 6% Ensagri Super S carbon black used to enhance electrode conductivity.
  • Ensagri Super S exhibits a nitrogen surface area of 44 m /g and a mean particle size of 47 nm.
  • the resulting dry mix was mixed with polyvinylidene difluoride (PVDF) and N- methylpyrolidinone (NMP) to give a spreadable slurry.
  • PVDF polyvinylidene difluoride
  • NMP N- methylpyrolidinone
  • the slurry was doctor bladed onto copper foil and dried at 80° C. Further drying was done in a vacuum oven at 120° C for 1 hour.
  • the composition of the resultant dry electrode was ca. 6% Super S, 5% PVDF and the remainder test carbon.
  • Electrode disks (0.005" thick) were fabricated into coin cells in an inert atmosphere dry box.
  • the assembled cell stack of the coin cell consisted of the carbon cathode, a IM UPF 6 ethylene carbonate (EC) /dimethyl carbonate (DMC) 1:1 (v/v) electrolyte saturated separator, and a lithium anode disk.
  • the carbon electrode was also saturated with electrolyte.
  • the coin cell was sealed with a polypropylene grommet by crimping the coin cell positive to the coin cell negative.
  • Stack pressure (ca. 250 psi) was delivered with a spacer and spring assembly. Cycling tests, voltage curves, and signature curve analysis:
  • Assembled coin cells were subjected to constant current discharge and charge between 0.002v and 2.0 v at room temperature or taper discharge under the same conditions. Between discharge and charge and subsequent discharge, cells were open circuited for 1000 sec. Current used for the tests ranged from C/50 to 2C. A C rate means that all the nominal capacity (mahr.) is delivered in one hour. Thus C/50 is all capacity in 50 hours and 2C is all capacity in 1/2 hour. In some cases the current is expressed as D/5 to indicate a cell discharge (lithium incorporated into the carbon). This is only done when the discharge and charge (lithium removed from the carbon) are at different current. If the rates for charge and discharge are the same then they are expressed as C rates.
  • Taper discharges were done by discharging at a constant current of C/2 or C followed by holding the cell at 0.002v for three hours during which time the current decreased from an initially high value (less than C rate) to near zero ma.
  • Taper charging (removal of lithium from the carbon) is a favorite charging method for commercial lithium ion cells.
  • a signature curve analysis was performed in addition to the above described cycling tests where voltage curves (cell voltage plotted versus time or capacity) and cycle life plots (capacity plotted versus cycle number) were recorded.
  • the coin cell is, after fully charging, subjected to a large constant current discharge to 0.002v, open circuited for 1000 sec, subjected to a smaller constant current discharge, open circuited, subjected to a smaller current and etc. This is done until the last discharge to 0.002v is at ca. C/40.
  • Accumulated discharge capacity is plotted versus discharge rate to give a signature curve. The plot is constructed such that the capacity at a particular rate is a summation of all the capacities for the previous higher rates.
  • the plot gives a very good indication of the rate capability of the test material.
  • the dQ/dV versus voltage plot is an essential equation of state indicator. In this plot, peaks represent voltage plateaus in the voltage curve where for example first order phase transformations occur. This can be seen for graphite where stages are observed. Sloping dQ/dV vs V curves are indicative of a continuous distribution of energy states within the test material.
  • DQ/dV curves for taper discharged cells are not given as the decreasing current and subsequent increase in voltage makes the differential plots confusing to view.
  • a certain amount of electrode fabrication, cell fabrication, and rate and method of discharging optimization was done on the three carbon materials so that as near complete as possible characterization of the materials could be dete ⁇ riined. The variations in testing will be described below for the individual cases. All tests were done on duplicate coin cells so that reproducibidility was within 5% in capacity. Data for duplicate cells are not always shown.
  • Figure 1 shows cycle life curves for three different sets of cells made with this carbon.
  • LaO 1 was initially discharged and charged at a C/50 rate followed by a cycle at C/12 then 3 cycles at d/7 and C/2 then cycled at d/2 and C/6 until the end of test.
  • Figure 2 shows la 17 where the first 5 cycles were with a d/2 taper discharge and a C/10 charge. Cycles 6 to 24 were at C/15 constant current discharge and charge then back to taper discharge and constant current charge at d/2 and C/10 until end of test.
  • Figure 3 shows data for la22 which was a signature curve test where the first two cycles were taper discharge at a d rate and constant current charge at C/12. Cycle 3 was a signature discharge with C/l 2 charging., as were cycles 9 and 15. All other cycles were as for cycles 1 and 2. What can be seen from Figures 1 to 3 is that the first cycle irreversible,
  • Qirrev and reversible, Qrev capacities are dependent upon the first discharge rate, and the first cycle charge efficiencies, (1st discharge capacity/1 st charge capacity x 100%) are independent of the first discharge rate.
  • Delivered discharge capacity at a d/2 or better rate is increased by a faster first cycle discharge.
  • this increased capacity is not lost by lower rate cycling as shown by the data of lal 7, Figures 1 and 2.
  • the first cycle discharge results in not only reversible incorporation of lithium into the carbon but also irreversible consumption of lithium most of which is associated with the passivation of the carbon surface to further electrolyte cathodic decomposition. This is quantified by the first cycle efficiency which is tabulated below.
  • first cycle irreversible and reversible specific capacities are listed along with high and low rate reversible cycling specific capacities.
  • specific energy densities are listed in brackets. These values are computed assuming the carbons are matched as anodes in an ion cell with a UCo0 2 cathode.
  • Figure 4 depicts the voltage curves for the above three cells.
  • the discharge and charge curves are sloping with an average voltage of ca. 0.65 volts vs lithium.
  • For cells lal 7 and la22 one can see the voltage drop with the taper discharge followed by the voltage rebound when the constant voltage discharge takes over for the last three hours.
  • La22 shows a rapid dip in voltage followed by a recovery during the d/1 constant current discharge part of the first cycle. It's companion cell showed the same feature although not as pronounced. This could be a lithium ion electrolyte starvation effect.
  • Figure 4 shows some hysteresis between charge and discharge. This is most pronounced for laO 1 and shows up as a bump in the charge curve at ca. 1.0 - 1.2 volts. This is less apparent in lal 7 and la22. This effect can be seen better in Figures 5 and 6 where the dQ/dV vs V curves for the first charge of laO 1 and la22 are shown. The peak at ca. 1.0 - 1.2 volt can clearly be seen and is more evident for the cell discharged at the lower rate, laO 1. This feature is still present at later cycle numbers as is shown by Figures 7 and 8 which are for cycle # 20 for laO 1. Figure 7 shows the reversibility of laO 1. The ca. 1.0 - 1.2 volt peak in the dQ/dV vs v curves could indicate some phase change or ordering or lithium association with some "special carbons" or heteroatoms, ie., H, S, or O.
  • Figure 9 shows the voltage curve for la22 at cycle 46.
  • the feature at 1.0 - 1.2 volts is there.
  • Figures 10 and 11 show signature curves for la21 and 22 at cycle 3, 9 and 15. Both cells were cycled the same way with a first cycle taper discharge at d/1 constant current followed by constant voltage discharge for three hours at 0.002v. Charging was at a constant current of C/12. Both cells show quite a strong dependence of capacity on rate and small loss of rate capability with cycle number.
  • the rate capability of la21 and 22 is as good or somewhat better than for commercial MCMB over the range C/10 - C/3.
  • capacity at C/3 is 82% of that at C/10.
  • capacity at C/3 is 82% of that at C/10.
  • commercial MCMB as shown in Figure 12 the same value is 74%.
  • Data from Table 2 and Figures 12 and 13 where the cycle life and voltage curve of commercial MCMB carbon are shown indicate that the cycle life, reversible capacity and rate capability of Carbon A compare favorably with commercial MCMB. The latter does have a somewhat better first cycle capacity efficiency and relatively flat voltage curve, Figure 13, with a lower average voltage, however, Carbon A has a larger reversible capacity.
  • the specific energy densities of la22 compare quite well with those of the MCMB.
  • Carbon A does have a larger first cycle irreversible specific energy density and a smaller first cycle reversible specific energy density but its low rate reversible specific energy density is larger, 1308 compared to 1232 mWhr/g.
  • High rate (d/2 or better) reversible cycling data for MCMB is not currently available but based on the low rate data it is expected that Carbon A will compare well.
  • Figure 14 shows the staging of the graphitic MCMB.
  • Figures 12 - 14 show the sensitivity of the MCMB to electrode fabrication.
  • Cell ulO 1 had an electrode densified at 1250 psi while ul05 had no densification. This means that Carbon A in anodes (tested versus U-metal cathode) can provide superior reversible capacity to commercial MCMB (first cycle, high rate, and low rate with minimal fade upon extended cycling); although, its 1 st cycle efficiency is slightly lower.
  • Example 2 Example 2:
  • Figure 16 shows the first voltage curve for these two cells.
  • the voltage curves are sloping with an average voltage near 0.65v.
  • Figure 17 shows the cycle 25 voltage curve while Figure 18 shows the dQ/dV vs v curves for the cycles of Figure 16 and 17 for la04.
  • the non- heat treated carbon Carbon A discussed above, there is a feature in the dQ/dV vs v curve on the first cycle but for the 1500°C heat treated material it is at 0.8V, is predominantly in the discharge and it is not present at later cycles. In this case, this voltage feature is associated with the formation of the passivation film.
  • Figures 19 and 20 show signature curve data for cells la23 and la24 which were cycled at C/10 for ten cycles then a signature curve was obtained at cycle 11. After more C/10 cycling signature data was obtained at cycles 17 and 23. From cycle 24 on, cycling was at C/10. There is a fairly strong dependence of capacity with rate but little loss of rate capability with cycle number. Comparison data is available for a commercial petroleum coke as shown in Table 3 and Figure 21 for cell pcO 1. At C/20, C/3, and a C rate the relative normalized capacities are 1, 0.82, and 0.65. For la23 these values are 1, 0.85, and 0.72.
  • Figure 22 shows the voltage curves for the first and 30th cycles of cell pcOl with commercial petroleum coke while Figure 23 shows the companion dQ/dV vs v curves.
  • the 1500oC heat treated carbon Anode Carbon B essentially behaves like commercial petroleum coke.
  • FIG. 24 shows cycling data for three representative cell sets made with this carbon material.
  • the cells were cycled in different ways. The cycling regimes are shown better in Figures 25, 26, and 27.
  • la06 was cycled at C/10 for 9 cycles then at d/3 and C/5 and finally at d/6 and C/3. Fade rates were low under these conditions but reversible capacity was lower than commercial MCMB.
  • Lal 5 used electrodes that were fabricated in a different way to that described above.
  • the cell was cycled at C/10 then d/1 and C/5 with periodic C/5 cycling.
  • Lal9 was taper discharged at d/2 and charged at C/10. This first cycle treatment has resulted in the best performance for this material.
  • FIG 31 shows ⁇ comparison of cycle 1 and cycle 10 for lal 9.
  • the charge efficiency for cycle 10 is near 100% and the cell impedance has decreased.
  • Figures 32 and 33 show signature curve data for la25 and 26 where signature data are collected at cycles 3, 9 and 15. Cycling was at C/10 for all other cycles. Data are similar for both cells except for the 3rd cycle curve of la26. This cell performed better at later cycles. The capacity is strongly dependent upon rate but little rate capability is lost with cycling. To compare to MCMB, capacity at C/3 is 90% of that at C/10 for la25 and 82% for MCMB.
  • Part B Testing of Carbons A and C in Anodes Versus Uthium Metal Oxide Cathode (U-ion cell)
  • Carbons A and C were used to fabricate electrodes which were used in coin cell hardware as anodes with UCo0 2 cathodes and liquid organic electrolyte. All voltage curves are cell voltages and are not referenced to lithium metal.
  • the test carbons were fabricated into electrodes in the following general way.
  • the test carbon powder was dry mixed with ca. 6% Super S carbon black used to enhance electrode conductivity.
  • the resulting dry mix was mixed with polyvinylidene difluoride (PVDF) and N-methylpyrrolidinone (NMP) to give a spreadable slurry.
  • PVDF polyvinylidene difluoride
  • NMP N-methylpyrrolidinone
  • the composition of the resultant dry electrode was ca. 6% Super S, 5% PVDF and the remainder test carbon.
  • UCo0 2 cathodes were fabricated in a similar way. Here the Super S carbon content was 10%.
  • Anodes were punched from the above dry electrode spreads as 0.5" dia. disks and in most cases and except where noted were densified by pressing with 2500 psi. Anode electrode disks (0.001" thick) and cathode electrode disks (0.003" thick) were fabricated into coin cells in an inert atmosphere dry box. Cathode electrodes this thin were required to allow C rate charging, consequently the anode electrodes are thinner than used in the previously reported carbon evaluations versus lithium electrodes.
  • the assembled cell stack of the coin cell consisted of the carbon anode, a IM UPF 6 ethylene carbonate (ECVdimethyl carbonate(DMC) 1:1 (v/v) electrolyte saturated separator, and a UCo0 2 cathode.
  • the carbon and UCo0 2 electrodes were also saturated with electrolyte.
  • the coin cell was sealed with a polypropylene grommet by crimping the coin cell positive to the coin cell negative.
  • Stack pressure (ca. 250 psi) was delivered with a spacer and spring assembly.
  • Uthium ion cells as opposed to Kthium metal cells are constructed in the discharged state.
  • the cathode, UCo0 2 is fully lithiated and has an open circuit potential versus lithium metal of ca. 4.0 volts.
  • the anode, in this case carbon is fully de-lithiated and has an open circuit voltage of between 2 and 3 volts versus lithium metal. Consequently the open circuit voltage of a lithium ion cell before charging is less than 2 volts, the difference between the voltage of each electrode relative to lithium metal.
  • the first charge of the lithium ion cell de- lithiates the cathode producing U,. x Co0 2 and lithiates the anode.
  • the material balance of the cell is chosen so that the carbon is fully lithiated on charge to near UC 6 and the cathode is de-lithiated so that x is less than 0.5. Removal of more lithium than this will result in rapid cathode failure.
  • To achieve these lithium balances on the first charge one must know the reversible and irreversible capacities of the anode. These values were approximated by previous tests in lithium ion cells. Assembled coin cells were subjected to constant current discharge and charge between 2.GV and 4.0v at room temperature or taper charge under the same conditions. Between discharge and charge and subsequent discharge, cells were open circuited for 1000 sec.
  • FIG 34 presents cycle life data for the best performance ion cell, la31, charged at a C rate and discharged at a D/5 rate. Except for the first cycle the charge capacity has been limited to ca. 330 mahr/g. This corresponds to an ion cell voltage of 4.0 v. This limit has been imposed to ensure that the anode does not go below 0.0 v versus lithium and deposit lithium metal. The first few cycles of the cell were used to establish this limit. From the figure one can see the fade rate is extremely low. Over the first twenty cycles the discharge capacity of the cell increases and eventually is larger than the charge capacity.
  • Figures 35 and 36 present similar data for two other lithium ion cells made with this carbon as an anode, la32 and la33. Here the charge and discharge capacity are the same and capacity fades with cycle number.
  • Figure 37 presents s ⁇ nilar data for a mesophase microbead anode lithium ion cell, la30.
  • Figure 38 presents discharge cycle life data as a comparison between Carbon A carbon anode and mesophase microbead anode lithium ion cells. Over the first 100 cycles the capacities of both cells were similar. After 100 cycles the microbead cell began to fade. For this cell, la31, the cycle life is longer than for the microbead anode.
  • Table 5 summarizes the cycle life data.
  • the first cycle efficiencies are lower than found in the lithium metal cell. To some extent, this is due to the difficulty in setting the cell upper voltage and capacity limit. There is no reason to expect this irreversible capacity to be different from that found in the lithium metal cell.
  • the discharge capacities at high rate are sn-nilar. Due to the microbead cell having ⁇ higher average voltage ca. 3.6 v and the inventive cells, 3.0 v, the former has a higher energy density in mWhr/g.
  • the cell voltages can be seen in Figures 39 to 41.
  • the inventive carbon cells la31 and la32 the voltage curves show capacity evenly from 2.0 to 4.0 volts while the microbead cell, la30, Figure 41, has most of the capacity near 3.8 volts with some down to 2.5 volts. With these cells the cell impedance increases with cycle number as the capacity decreases.
  • Figures 42 and 43 present signature curve data for inventive carbon cell la31 and microbead cell la30 respectively.
  • Signature curve data are collected at cycle 205, 220 and 240 for each cell.
  • the rate performance of the inventive carbon cell la31 is excellent.
  • the charge cycle before the signature cycle was ca. 340 mahr which is delivered on the subsequent discharge steps at rates greater than C/2.
  • the signature data is collected by charging the cell followed by discharge steps at rates of 2C, C, C/1.25, C/1.5, C/2, C/3, etc. down to C/40.
  • the signature curve for rates of 2C to C/2 or C/3 is correct, for rates lower than this it may be suspect.
  • Figure 43 shows similar data for the microbead cell.
  • the rate capability is also excellent in that all the available capacity is delivered at high rates, however the overall delivered capacity is lower than for the inventive carbon cell.
  • Figures 49 and 50 present cell voltage plots of the inventive carbon anode and mesophase microbead anode cells respectively. Here again as was found with the lithium metal cells the voltage plots for both materials is similar. With cycle life the cell impedance increases leading to capacity loss. With la37, Figure 50 at cycles 60 and 115 one can see the cell shunting on charge.
  • the low temperature carbon, Carbon A performs as well in the lithium ion cell as it does in the lithium metal cell.

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne des batteries aux ions de lithium, et plus particulièrement des électrodes perfectionnées dans des accumulateurs aux ions de lithium. Lesdites électrodes contiennent des noirs de carbone spécifiques, tels que des noirs de carbone thermiques.
PCT/US1998/003408 1997-02-26 1998-02-20 Utilisation de noir de carbone comme materiau anodique pour accumulateurs aux ions de lithium WO1998038685A2 (fr)

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AU65359/98A AU6535998A (en) 1997-02-26 1998-02-20 Use of thermal carbon black as anode material for lithium-ion batteries

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US97953397A 1997-11-26 1997-11-26
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Publication number Priority date Publication date Assignee Title
CN114156472A (zh) * 2020-11-24 2022-03-08 宁德新能源科技有限公司 电化学装置和电子装置
WO2023072918A1 (fr) 2021-10-26 2023-05-04 Carbonx B.V. Nouveau matériau d'anode pour batteries au lithium et au sodium

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CN107305941B (zh) * 2016-04-21 2019-12-27 中国科学院苏州纳米技术与纳米仿生研究所 锂-碳复合材料、其制备方法与应用以及锂补偿方法

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EP0205856B1 (fr) * 1985-05-10 1991-07-17 Asahi Kasei Kogyo Kabushiki Kaisha Batterie secondaire
US5028500A (en) * 1989-05-11 1991-07-02 Moli Energy Limited Carbonaceous electrodes for lithium cells
BR9305623A (pt) * 1992-08-27 1995-03-07 Cabot Corp Negro-de-fumo e composição de matéria
JP2991884B2 (ja) * 1993-02-16 1999-12-20 シャープ株式会社 非水系二次電池
JP3259930B2 (ja) * 1993-03-11 2002-02-25 財団法人電力中央研究所 リチウム二次電池
US5571638A (en) * 1993-09-30 1996-11-05 Sumitomo Chemical Company Limited Lithium secondary battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114156472A (zh) * 2020-11-24 2022-03-08 宁德新能源科技有限公司 电化学装置和电子装置
CN114171739A (zh) * 2020-11-24 2022-03-11 宁德新能源科技有限公司 电化学装置和电子装置
CN114156472B (zh) * 2020-11-24 2023-07-28 宁德新能源科技有限公司 电化学装置和电子装置
CN114171739B (zh) * 2020-11-24 2023-08-01 宁德新能源科技有限公司 电化学装置和电子装置
WO2023072918A1 (fr) 2021-10-26 2023-05-04 Carbonx B.V. Nouveau matériau d'anode pour batteries au lithium et au sodium

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