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WO1997048645A1 - Materiau electrode ameliore pour cellule electrochimique et procede de fabrication - Google Patents

Materiau electrode ameliore pour cellule electrochimique et procede de fabrication Download PDF

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Publication number
WO1997048645A1
WO1997048645A1 PCT/US1997/009778 US9709778W WO9748645A1 WO 1997048645 A1 WO1997048645 A1 WO 1997048645A1 US 9709778 W US9709778 W US 9709778W WO 9748645 A1 WO9748645 A1 WO 9748645A1
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WO
WIPO (PCT)
Prior art keywords
heating
precursor material
transition metal
phase
lithium
Prior art date
Application number
PCT/US1997/009778
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English (en)
Inventor
Zhenhua Mao
Original Assignee
Motorola Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Motorola Inc. filed Critical Motorola Inc.
Publication of WO1997048645A1 publication Critical patent/WO1997048645A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Complex oxides containing cobalt and at least one other metal element
    • C01G51/42—Complex oxides containing cobalt and at least one other metal element containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Complex oxides containing nickel and at least one other metal element
    • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/04—Compounds with a limited amount of crystallinty, e.g. as indicated by a crystallinity index
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

  • This invention relates in general to secondary rechargeable electrochemical cells, and more particularly to secondary lithium electrochemical cells having high capacity positive electrodes.
  • Lithiated transition metal oxide batteries are being studied as an alternative to current nickel- cadmium and nickel-metal hydride cells because they possess several attractive characteristics, e.g. high cell voltage, long shelf life, a wide operating temperature range, and use of relatively non-toxic materials.
  • Patent Nos. 4,302,518 and 4,357,215 both to Goodenough, et al. These materials have been intensively investigated and one of them, lithium cobalt oxide is currently used in commercial lithium ion batteries. Numerous patents have been issued for different improvements in these materials as the positive electrode for lithium cells. An example of a recent improvement is illustrated in U.S. Patent No. 5,180,547 to VonSacken for "HYDRIDES OF LITHIATED NICKEL DIOXIDE AND SECONDARY CELLS PREPARED THEREFROM". The VonSacken reference teaches fabricating the hydroxides of lithium nickel dioxide fabricated in an atmosphere including a partial pressure of water vapor measuring about 2 torr.
  • each material is synthesized in an oxidizing environment such as O2 or air using nickel or cobalt and lithium containing salts.
  • an oxidizing environment such as O2 or air using nickel or cobalt and lithium containing salts.
  • a publication to Ohzuku, et al published in the Journal of the Electrochemical Society, Vol. 140, No. 7, July 19, 1993, illustrates at Table I thereof the special processing methods for preparing lithiated nickel oxide.
  • Each of the methods illustrated in the Ohzuku, et al reference show preparing the material in an oxidizing environment of either oxygen or air.
  • Charge and discharge of the materials fabricated according to these processes proceeds by a charge mechanism of deintercalation and intercalation of lithium ions from and into these materials.
  • the materials synthesized by the prior art methods have a reversible capacity on the order of approximately 135 milliamperes (mAh/g). In other words, about 0.5 lithium ions can be reversibly deintercalated and intercalated from and into each mole of lithiated nickel oxide or lithiated cobalt oxide.
  • a significant amount of the capacity of these materials resides at potentials higher than about 4.2 volts versus lithium. If more than 0.5 lithium ions is removed from each of either lithiated nickel oxide or lithiated cobalt oxide, potentials higher than 4.2 volts versus lithium are required causing decomposition of most electrolytes. Further, removal of more than 0.5 lithium ions will result in irreversible changes to the structure of these materials, causing a decrease in the capacity during charge and discharge cycles. This result was reported in a publication by Xie, et al, presented at the Electrochemical Society Fall Meeting, 1994, Extended Abstract No. 102, Miami, Florida, October, 1994.
  • Reversible capacities of the most commonly used materials synthesized in O2 and air atmospheres are very sensitive to residual, active lithium salts, such as Li2 ⁇ , LiOH, and LiC ⁇ 3, each of which result from the synthesis process.
  • the prior art processes tend to result in a single phase crystalline material, such as a single phase crystalline lithiated nickel oxide material. It is hypothesized that these artifacts of the prior art preparation process result in materials which have lower capacities than might otherwise be expected. Accordingly, there exists a need to develop a new cathode material for rechargeable electrochemical systems which is fabricated of materials that are relatively environmentally friendly, may be fabricated at low temperatures, and which demonstrate performance characteristics superior to those of the prior art.
  • Such materials should have higher capacity, i.e., greater than about 200 mAh/g at potentials of between 3.0 and 4.2 volts versus a Li metal. Such materials should also have a relatively easy synthesis process which is highly controllable, and which demonstrates insensitivity to residual lithium salts. Finally, the material should have a high initial charge efficiency and be highly reversible charge/discharge reaction so as to provide a material of good cycle life.
  • FIG. 1 is a schematic representation of an electrochemical cell including an electrode in accordance with the instant invention
  • FIG. 2 is a flowchart illustrating the steps for preparing a lithiated transition metal oxide material in accordance with the instant invention
  • FIG. 3 is a charge, discharge and recharge curve for a material, in accordance with the instant invention.
  • FIG. 4 is a chart illustrating discharge capacity versus cycle number for an AA cell with a positive electrode material, in accordance with this invention.
  • FIG. 1 there is illustrated therein a schematic representation of an electrochemical cell 10 including a lithiated transition metal oxide electrode in accordance with the instant invention.
  • the electrochemical cell includes a positive electrode 20 and a negative electrode 30 and has an electrolyte system 40 disposed therebetween.
  • the electrochemical cell 10 further includes a positive electrode fabricated of a transition metal oxide such as a nickel oxide or a cobalt oxide electrochemical charge storage material which is described in greater detail hereinbelow.
  • the negative electrode 30 or anode of the cell may be fabricated from a material selected from the group consisting of, but not limited to, lithium metal, lithium alloying metals, such as aluminum, tin, and bismuth, carbon (including graphite and petroleum coke), low voltage lithium intercalation compounds such as TiS2, V6O13, M0S2, and combinations thereof.
  • the negative electrode 30 may be fabricated of the pyrolysis reaction product of multifunctional organic monomers, such as is disclosed in, for example, U.S. Patent Application No. 08/534,427 by Zhang, et al, entitled “Carbon Electrode Materials for Electrochemical Cells and Method of Making Same", filed September 27, 1995; U.S. Patent Application Serial No.
  • the electrolyte may be either a solid, a gel, or a liquid electrolyte system. Further, the electrolyte may be either an aqueous or nonaqueous electrolyte system.
  • the electrolyte 40 may also act as a separator between a positive and negative electrodes.
  • the electrolyte is fabricated of a material such as is disclosed in commonly assigned copending U.S. Patent Application Serial No. 08/518,732 entitled Blended Polymer Gel Electrolytes in the name of Oliver, the disclosure of which is incorporated herein by reference, as well as U.S. Patent Application Serial No. 08/638,706 entitled Polymer Gel Electrolytes, to Oliver, et al. filed April 29, 1996.
  • a method for fabricating a lithiated transition metal oxide material which is capable of storing and discharging electrical charge. The material disclosed herein is therefore useful as the cathode in lithium rechargeable batteries.
  • the stabilized material has the formula Li x TMy ⁇ 2, where TM is a transition metal selected from the group of nickel or cobalt and combinations thereof; 0.98 ⁇ x ⁇ l.l; and 0.98 ⁇ y ⁇ l.l
  • the electrode material is a multiphase electrode material having at least one phase which is a substantially crystalline phase having the formula LiTM ⁇ 2 and having a second phase being substantially amorphous.
  • the amorphous phase comprises between 10 and 50% of the total electrode material.
  • Other phases of crystalline, microcrystalline, polycrystalline or amorphous material may also be included in the electrode material.
  • the electrode material may further include one or more modifiers selected from the group of titanium, bismuth, iron, zinc, chromium, and combinations thereof.
  • the electrode material is LiNi ⁇ 2, and includes a first crystalline phase having the formula LiNi ⁇ 2, and a second substantially amorphous phase which is Li rich as compared to Ni.
  • the amorphous phase comprises between 20 and 35% of the material.
  • the flowchart 50 illustrates at box 52 the step of providing a first precursor lithium containing material sml.
  • the lithium containing precursor material is a nitrate salt and hence is preferably lithium nitrate.
  • Box 54 illustrates the step of providing a second precursor material sm2.
  • the second precursor material is preferably a transition metal hydroxide, and in the embodiment in which the end product is a lithiated nickel oxide, the starting material provided at Box 54 is a nickel hydroxide.
  • This specific nickel hydroxide material can be any one of a number of a different types of materials, and in one preferred embodiment is an "aged" ⁇ -phase nickel hydroxide material.
  • the material provided at Box 54 may be selected from the group consisting of NiO, NiC ⁇ 3, Ni(N ⁇ 3)2 • 6H2O, Ni(OH)2, CoO, Co(OH)2, and combinations thereof.
  • Step 56 of FIG. 2 is the step of mixing the precursor materials provided at Boxes 52 and 54.
  • the mixing should be complete, and may be carried out in commonly used mixing devices.
  • the materials are reacted, as by heating, as described in Box 58 of flowchart 50.
  • the conditions and environments in which the heating takes place is important to forming material having a high capacity as illustrated herein. More particularly, the mixed materials are heated in an inert environment. By an inert environment, it is meant that the principal components of the atmosphere in which the heating takes place are not reactive with the precursor materials therein. Accordingly, the heating illustrated in step 58 of Flowchart 50 is carried out in a helium, nitrogen, or argon environment.
  • the heating generates reaction conditions, and preferably takes place in a nitrogen atmosphere at temperatures of about 500-800°C.
  • a temperature Ti for a first period of time, Xi.
  • Ti is typically between about 200-400°C, while Ri is typically a first rate and is on the order of 2-5° per minute.
  • the mixed precursor material may be placed directly into an oven preheated to Ti, from room temperature. Thereafter, the materials are held at temperature for a period of time, Xi, between approximately 1 and 10 but preferably three hours time. It is important to note that the next step 58 takes places in an inert atmosphere..
  • X2- T2 is typically on the order of approximately 500-650°C, and preferably about 610°C.
  • X2 is a time period which is typically on the order of between 5 and 40 hours and preferably about 20 hours.
  • the oven is ramped from Ti to T2 at a rate of approximately between 1 and 10° per minute, and preferably about 2° per minute. This heating is maintained under the inert atmosphere described hereinabove with respect to step 58.
  • material may be added to the heating at this step and time as is illustrated by Box 62.
  • the materials are cooled to room temperature and subjected to a grinding and mixing process which may be carried out in a conventional mill. Thereafter, the materials may be taken from room temperature up to temperature T3, which is typically between 600-700°C and preferably about 650°C. Thereafter, the materials are heated in air for a certain period of time X3 of between 1 and 20 hours and preferably approximately 8 hours. This step is illustrated by box 66 of FIG. 2 and is preferably carried out in an air atmosphere. Alternatively, after the cooling and grinding steps such as that shown in Box 64, the materials may be introduced into an oven already at temperature T3 and in an air environment.
  • a mixture of 500 grams (g) of spherical "aged” ⁇ -phase Ni(OH)2 and 297g of LiN ⁇ 3 was heated at 300°C for 3 hours in He and then heated further at 610°C for 15 hours in He. An additional 74g LiN03 was then added to the resulted mixture and mixed/ground. The mixture was then heated at 610°C in He for 15 hours. After that, the material was ground and heated at 650°C in air for 8 hours to form the desired material. The material was then ground and mixed with 6 wt% carbon black and 5 wt% polytetrafluoroethylene (PTFE) and rolled to form a film.
  • PTFE polytetrafluoroethylene
  • Li metal foil was used as the negative electrode
  • porous polypropylene was used as the separator
  • the electrolyte was 1 M LiPF6 solution in 50% propylene carbonate (pc) and 50% ethylene carbonate (ec).
  • FIG. 3 shows that the material has a capacity of 233 milliamperes hours/gram (mAh/g) within the potential window of 3 to 4.3 volts and an initial charge efficiency of about 94%.
  • a material made by a conventional method would have a capacity of less than 200 mAh/g and an initial charge efficiency of less than 86%.
  • Example HI A mixture of Ni(OH)2 and LiN ⁇ 3 was heated in the same manner as in Example I except that the starting material Ni(OH)2 was "flake” like regular ⁇ - phase. The resulted material showed an initial capacity of 217 mAh/g with an initial charge efficiency of 90%.
  • Example HI A mixture of Ni(OH)2 and LiN ⁇ 3 was heated in the same manner as in Example I except that the starting material Ni(OH)2 was "flake” like regular ⁇ - phase. The resulted material showed an initial capacity of 217 mAh/g with an initial charge efficiency of 90%.
  • a mixture of 500 of spherical "aged” ⁇ -phase Ni(OH)2 and 315g of LiN ⁇ 3 was heated in He at 300°C for 4 hours and then heated at 610°C for 15 hours also in He.
  • the resulted material was then mixed with an additional 56g of LiN ⁇ 3 and heated in He at 610°C for 10 hours.
  • the material was then ground and heated in air at 650°C for 6 hours.
  • the resulting material was tested as the cathode material in an experimental cell and showed an initial capacity of 228 mAh/g and an initial charge efficiency of 93%.
  • Example I A mixture of the material as given in Example I and 6 wt% graphite and 4 wr% polyvinylidene fluoride (PVDF) with N-Methyl-2-Pyrrolidone (NMP) as the solvent was cast on an Al foil and formed into a film. The film was then cut and rolled together with a graphite film as the negative electrode, a lMLiPF ⁇ solution in 50% PC and 50% EC as electrolyte and a porous polypropylene as the separator and placed in a steel can conventionally called AA size. The cell was then charged and discharged within the cell voltage window of 2.5 to 4.2 volts at room temperature.
  • FIG. 4 presents the capacity of the cell as a function of cycle number.
  • the initial capacity of the cell was about 820 mAh.
  • 98% of the initial capacity was still retained.
  • AA cells made with equivalent amounts of conventional materials such as LiCo ⁇ 2 or LiNi ⁇ 2 fabricated by prior art methods as the positive electrode material have a capacity of about 600 mAh. Therefore, this example illustrates that the capacity of A A cells can be increased by greater than 30% by using the instant material.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Procédé pour préparer un matériau en oxyde métallique de transition au lithium à mémoire de charge électrochimique utilisable pour une cellule électrochimique. La cellule (10) est composée d'une cathode (20), d'une anode (30) et d'un électrolyte (40) placé entre les deux. Le procédé comprend la préparation du matériau en oxyde métallique de transition au lithium dans un environnement inerte. Ces matériaux se caractérisent par une performance électrochimique améliorée et une composition multiphasée dans laquelle au moins une des phases est sensiblement cristalline, tandis qu'une seconde phase est sensiblement amorphe.
PCT/US1997/009778 1996-06-17 1997-06-05 Materiau electrode ameliore pour cellule electrochimique et procede de fabrication WO1997048645A1 (fr)

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US66341596A 1996-06-17 1996-06-17
US08/663,415 1996-06-17

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003086975A1 (fr) * 2002-04-08 2003-10-23 Council Of Scientific And Industrail Research Procede de preparation de materiau pour cathodes de piles au lithium
US6953566B2 (en) 2002-03-29 2005-10-11 Council Of Scientific & Industrial Research Process for preparing cathode material for lithium batteries
WO2006037205A1 (fr) * 2004-10-01 2006-04-13 Inco Limited Procede de production d'oxydes de metaux de transition au lithium
US20110143209A1 (en) * 2009-12-11 2011-06-16 Park Do-Hyung Positive electrode active material for lithium battery and lithium battery using the same
US9581875B2 (en) 2005-02-23 2017-02-28 Sage Electrochromics, Inc. Electrochromic devices and methods

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5449577A (en) * 1994-01-28 1995-09-12 Moli Energy (1990) Limited Method for increasing the reversible capacity of lithium transition metal oxide cathodes
US5531920A (en) * 1994-10-03 1996-07-02 Motorola, Inc. Method of synthesizing alkaline metal intercalation materials for electrochemical cells

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5449577A (en) * 1994-01-28 1995-09-12 Moli Energy (1990) Limited Method for increasing the reversible capacity of lithium transition metal oxide cathodes
US5531920A (en) * 1994-10-03 1996-07-02 Motorola, Inc. Method of synthesizing alkaline metal intercalation materials for electrochemical cells

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMISTRY EXPRESS, 1990, Vol. 5, No. 10, OHZUKU T., "Preliminary Results on Synthesis ... Rechargable Lithium Cells", pages 733-36. *
CHEMISTRY EXPRESS, 1991, Vol. 6, No. 3, OHZUKU T., "Synthesis and Characterization of ... Nonaqueous Cells", pages 161-4. *
J. ELECTROCHEM. SOC., Vol. 140, No. 7, July 1993, OHZUKU T., "Electrochemistry and Structural Chemistry ... Secondary Lithium Cells", pages 1862-70. *
OHZUKU T., "Lithium Batteries, New Materials Developments and Perspectives", ELSEVIER, NEW YORK, 1994, Chapter 6, pp. 239-80. *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6953566B2 (en) 2002-03-29 2005-10-11 Council Of Scientific & Industrial Research Process for preparing cathode material for lithium batteries
WO2003086975A1 (fr) * 2002-04-08 2003-10-23 Council Of Scientific And Industrail Research Procede de preparation de materiau pour cathodes de piles au lithium
WO2006037205A1 (fr) * 2004-10-01 2006-04-13 Inco Limited Procede de production d'oxydes de metaux de transition au lithium
JP2008514537A (ja) * 2004-10-01 2008-05-08 シーブイアールディ、インコ、リミテッド リチウム遷移金属酸化物の製造方法
KR100849279B1 (ko) * 2004-10-01 2008-07-29 베일 인코 리미티드 리튬 전이 금속 산화물의 제조 방법
AU2005291782B2 (en) * 2004-10-01 2009-04-23 Vale Canada Limited Process for producing lithium transition metal oxides
US9581875B2 (en) 2005-02-23 2017-02-28 Sage Electrochromics, Inc. Electrochromic devices and methods
US10061174B2 (en) 2005-02-23 2018-08-28 Sage Electrochromics, Inc. Electrochromic devices and methods
US11567383B2 (en) 2005-02-23 2023-01-31 Sage Electrochromics, Inc. Electrochromic devices and methods
US20110143209A1 (en) * 2009-12-11 2011-06-16 Park Do-Hyung Positive electrode active material for lithium battery and lithium battery using the same
US8586247B2 (en) * 2009-12-11 2013-11-19 Samsung Sdi Co., Ltd. Positive electrode active material comprising an agglomeration of at least two primary particles for lithium battery and lithium battery using the same

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