CN1059757C - Secondary battery with lithium ion aqueous solution - Google Patents

Secondary battery with lithium ion aqueous solution Download PDF

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Publication number
CN1059757C
CN1059757C CN93108612A CN93108612A CN1059757C CN 1059757 C CN1059757 C CN 1059757C CN 93108612 A CN93108612 A CN 93108612A CN 93108612 A CN93108612 A CN 93108612A CN 1059757 C CN1059757 C CN 1059757C
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Prior art keywords
active material
cathode active
aqueous solution
anode
mol
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CN1097526A (en
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杨华铨
陈凤翔
林炳雄
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Peking University
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Peking University
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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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a secondary battery with a lithium ion aqueous solution. A cathode active material of the secondary battery is a composite oxide of lithium and a transition element. A cathode uses metals with low activity and no harm to replace lithium or an alloy thereof. The secondary battery of the present invention avoids using a non-aqueous solution and a lithium salt containing harmful substances as electrolyte. An open circuit voltage of the secondary battery is similar to Ni/Cd/ and Zn/Mn batteries sold in market, and the secondary battery has the advantages of excellent reversibility, deep charge and discharge resistance and good application prospect.

Description

Secondary battery with lithium ion aqueous solution
The present invention relates to secondary battery with lithium ion aqueous solution, belong to the secondary cell field.
High-energy battery is subjected to extensive attention at present.The alkali metal transition elements composite oxides that the numerous and confused research of people is synthetic according to the topochemistry principle, for example LiCoO 2, LiNiO 2, LiV 3O 8Deng as cathode active material, form nonaqueous electrolyte battery or solid electrolyte cell (J, Electrochem.Soc.Vol.138, No.10, October 2859-2864,1991 as anode with lithium metal or lithium alloy; EP 0462575A2; EP0345707A1; U.S.P4804596; EP 0243926A1).Above-mentioned cathode substance good reversibility, stable performance.Form battery with it but make anode, can not work having under the condition of water with lithium or lithium alloy.Must adopt some organic solvent, for example ethylene carbonate (EC), propene carbonate (PC), dimethoxy-ethane (DME) or acrylate (MA) etc., perhaps their mixture and some lithium salts, for example LiBF 4, LiAsF 6, LiClO 4, LiPF 6, LiCF 3SO 3Or LiN (CF 3SO 2) 2Be electrolyte, described lithium salts is difficult to obtain, and price is very high, by the conductive electrolyte solution performance that forms also lower.In addition, as anode, the fail safe of battery is relatively poor with lithium or lithium alloy, and lithium is a kind of very active metal, can with effects such as above-mentioned electrolyte solution generation oxidation, decomposition, make battery failure.Simultaneously in the charging of battery, discharge process, have dendritic growth, penetrate separator, can cause partial short-circuit, set off an explosion or firing accident, this existing bibliographical information.Such battery except requiring the waterless operation environment, also needs many special process and technology on making simultaneously.Although the open circuit voltage that the non-water lithium battery of above-mentioned secondary has can be up to 4 volts about, specific capacity is also bigger, for various reasons not seen widespread use so far.
The purpose of this invention is to provide a kind of novel secondary battery with lithium ion aqueous solution, and a series of new cathode active materials of described battery that are used for are provided.
Secondary battery with lithium ion aqueous solution of the present invention mainly comprises:
1, negative electrode: form by cathode active material, graphite and polytetrafluoroethylene, their weight ratio is 1: (2.5-5): (0.1-0.5), described cathode active material is: the composite oxides of lithium and transition elements, and the general formula of alternative this type oxide is respectively:
Li xM yN 1-yO 2 (I)
M represents one or both elements among Ni, Co, Mn, Fe, Cu or the Cr,
N represents Ni, Co, Mn, Fe, Cr, Zn or Cu,
0＜x≤1.3 0≤y≤0.5
Li 1-x′M′ y′N′ 2-y′O 4 (II)
M ' represents Fe, Cu, Co, Zn, Ni or Cr,
N ' mainly represents Mn,
0＜x′≤1.0 0≤y′≤1
2, anode: be metal M g, Ni or Zn;
3, electrolyte solution: be the lithium hydroxide aqueous solution of 4-5 mol;
Battery advantage of the present invention is:, avoided adopting the defective of above-mentioned lithium salts and with the inconvenience of organic solvent, used lower zinc of metallicity etc. to make anode, the fail safe that has improved battery greatly simultaneously as electrolyte solution with lithium hydroxide aqueous solution cheap and easy to get.And manufacturing process is also fairly simple easily.The specific capacity of this type of battery is 120-200mAhr/g (cathode active material), and open circuit voltage is similar with the Zn/Mn battery to commercially available Ni/Cd about the 1.5-2.0 volt, but has avoided making anode with harmful Cd, and good invertibity is arranged, and can stand to fill deeply, put deeply.
Among the present invention with aforementioned formula (I) or (II) expression cathode active material make with known method, that is: the carbonate of lithium and other required metals or nitrate or the predetermined mole of oxide are mixed, porphyrize made in 500-1000 ℃ of calcination 2-6 hour.Perhaps the nitrate aqueous solution with above-mentioned metal mixes by the mol ratio, adds sal volatile, obtains sediment, in 500-1000 ℃ of calcination.Also available other known method preparations.The compound that contains three kinds of transition elements in the general formula (I) is the new compound of a class.0≤y≤0.4 in the general formula (I), the compound of representative, or 0.2≤y '≤0.4 in the general formula (II), the compound of representative is as the cathode active material better effects if.
The method for making of battery of the present invention is: with cathode active material, graphite and polytetrafluoroethylene powder successively by its weight ratio 1: (2.5-5): (0.1-0.5) mix, be pressed into sheet on nickel screen, as negative electrode, its area is 5.0 square centimeters.Anode magnesium, nickel or zinc metal sheet.Alkaline-resisting material such as films such as polyester, rubber with the band micropore between cathode and anode separate.Electrolyte solution is the lithium hydroxide aqueous solution of 4-5 mol.
Brief Description Of Drawings:
Fig. 1,3,5,7,9,11 is the x optical diffraction analysis figure of respective cathode active matter.Ordinate is a peak intensity, and abscissa is 2 θ angles.
Fig. 2,4,6,8,10,12 is the charge and discharge curve chart of respective battery.Ordinate is the voltage voltage, and abscissa is the number of minutes.
In order to be illustrated more clearly in the present invention, enumerate following examples.But these do not have any restriction to the present invention.
Example 1
According to aforesaid battery method for making, name is consisted of Li 0.9Co 0.25Mn 1.75O 4Cathode active material, make negative electrode, and make anode with zinc metal sheet.Lithium hydroxide electrolyte aqueous solution concentration is 5 mol, makes battery.Its main performance is as follows:
Open circuit voltage: 1.25-1.50V
Average discharge volt: 1.15V
Ending discharge voltage: 0.90V
Discharge time: 165min (2mA/cm 2Constant current discharge)
Specific capacity: 138mAhr/g (cathode active material)
Wherein the x optical diffraction analysis of cathode active material the results are shown in Figure 1.
The charging and discharging curve of this battery is seen Fig. 2.
Example 2
According to aforesaid battery method for making, name is consisted of Li 0.9Fe 0.25Mn 1.75O 4Cathode active material, make negative electrode, and make anode with zinc metal sheet.Lithium hydroxide electrolyte aqueous solution concentration is 4.5 mol, makes battery.Its main performance is as follows:
Open circuit voltage: 1.25-1.50V
Average discharge volt: 1.20V
Ending discharge voltage: 0.90V
Discharge time: 150min (2mA/cm 2Constant current discharge)
Specific capacity: 125mAhr/g (cathode active material)
Wherein the x optical diffraction analysis of cathode active material the results are shown in Figure 3.
The charging and discharging curve of this battery is seen Fig. 4.Example 3
According to aforesaid battery method for making, name is consisted of Li 0.9Ni 0.27Co 0.73O 4Cathode active material, make negative electrode, and make anode with zinc metal sheet.Lithium hydroxide electrolyte aqueous solution concentration is 5 mol, makes battery.Its main performance is as follows:
Open circuit voltage: 1.50-2.00V
Average discharge volt: 1.30～140V
Ending discharge voltage: 0.90V
Discharge time: 240min (1.6-2.0mA/cm 2Constant current discharge)
Specific capacity: 200mAhr/g (cathode active material)
Wherein the x optical diffraction analysis of cathode active material the results are shown in Figure 5.
The charging and discharging curve of this battery is seen Fig. 6.
Example 4
According to aforesaid battery method for making, name is consisted of LiMn 0.2Ni 0.2Co 0.6O 4Cathode active material, make negative electrode, and make anode with zinc metal sheet.Lithium hydroxide electrolyte aqueous solution concentration is 5 mol, makes battery.Its main performance is as follows:
Open circuit voltage: 1.50-2.00V
Average discharge volt: 1.25V
Ending discharge voltage: 0.90V
Discharge time: 180min (1.6-2.0mA/cm 2Constant current discharge)
Specific capacity: 150mAhr/g (cathode active material)
Wherein the x optical diffraction analysis of cathode active material the results are shown in Figure 7.
The charging and discharging curve of this battery is seen Fig. 8.Example 5
According to aforesaid battery method for making, name is consisted of Li 0.7Fe 0.2Co 0.8O 4Cathode active material, make negative electrode, and make anode with zinc metal sheet.Lithium hydroxide electrolyte aqueous solution concentration is 5 mol, makes battery.Its main performance is as follows:
Open circuit voltage: 1.50-2.00V
Average discharge volt: 1.25V
Ending discharge voltage: 0.90V
Discharge time: 190min (1.6-2.0mA/cm 2Constant current discharge)
Specific capacity: 160mAhr/g (cathode active material)
Wherein the x optical diffraction analysis of cathode active material the results are shown in Figure 9.
The charging and discharging curve of this battery is seen Figure 10.Example 6
According to aforesaid battery method for making, name is consisted of Li 0.8Cr 0.25Mn 1.75O 4Cathode active material, make negative electrode, and make anode with zinc metal sheet.Lithium hydroxide electrolyte aqueous solution concentration is 4 mol, makes battery.Its main performance is as follows:
Open circuit voltage: 1.25-1.50V
Average discharge volt: 1.15V
Ending discharge voltage: 0.90V
Discharge time: 175min (1.6-2.0mA/cm 2Constant current discharge)
Specific capacity: 145mAhr/g (cathode active material)
Wherein the x optical diffraction analysis of cathode active material the results are shown in Figure 11.
The charging and discharging curve of this battery is seen Figure 12.

Claims (9)

1, the novel secondary battery with lithium ion aqueous solution of a class is characterized in that it comprises:
(1) negative electrode: by cathode active material, graphite and polytetrafluoroethylene, by weight 1: (2.5-5): (0.1-0.5), mix, on nickel screen, suppress forming, this cathode active material is the composite oxides of lithium and transition elements, represents by following general formula (I) or (II):
Li xM yN 1-yO 2 (I)
M represents one or both elements among Ni, Co, Mn, Fe, Cu or the Cr,
N represents Ni, Co, Mn, Fe, Cr, Zn or Cu,
0＜x≤1.3 0≤y≤0.5
Li 1-x′M′ y′N′ 2-y′O 4 (II)
M ' represents Fe, Cu, Co, Zn, Ni or Cr,
N ' mainly represents Mn,
0＜x′≤1.0 0≤y′≤1
(2) anode: be Mg, Ni or Zn
(3) electrolyte solution: be the lithium hydroxide aqueous solution of 4-5 mol;
2, by the described battery of claim 1, it is characterized in that described cathode active material is the compound of general formula (I) representative, the compound of 0≤y in the formula≤0.4 or general formula (II) representative, the 0.2≤y ' in the formula≤0.4;
3, by claim 1 or 2 described batteries, it is characterized in that described cathode active material is Li 0.9Co 0.25Mn 1.75O 4, anode is a zinc metal sheet, electrolyte solution is the lithium hydroxide aqueous solution of 5 mol;
4, by claim 1 or 2 described batteries, it is characterized in that described cathode active material is Li 0.9Fe 0.25Mn 1.75O 4, anode is a zinc metal sheet, electrolyte solution is the lithium hydroxide aqueous solution of 4.5 mol;
5, by claim 1 or 2 described batteries, it is characterized in that described cathode active material is LiNi 0.27Co 0.73O 2, anode is a zinc metal sheet, electrolyte solution is the lithium hydroxide aqueous solution of 5 mol;
6, by claim 1 or 2 described batteries, it is characterized in that described cathode active material is LiMn 0.2Ni 0.2Co 0.6O 2, anode is a zinc metal sheet, electrolyte solution is the lithium hydroxide aqueous solution of 5 mol;
7, by claim 1 or 2 described batteries, it is characterized in that described cathode active material is Li 0.7Fe 0.2Co 0.8O 2, anode is a zinc metal sheet, electrolyte solution is the lithium hydroxide aqueous solution of 5 mol;
8, by claim 1 or 2 described batteries, it is characterized in that described cathode active material is Li 0.8Cr 0.25Mn 1.75O 4, anode is a zinc metal sheet, electrolyte solution is the lithium hydroxide aqueous solution of 4 mol;
9, the preparation method of the described secondary battery with lithium ion aqueous solution of claim 1 to 8 is characterized in that, described method comprises:
(1) with general formula (I) or cathode active material (II), graphite powder and tetrafluoroethene powder successively by their weight ratio 1: (2.5-5): (0.1-0.5), mix, on nickel screen, be pressed into sheet as negative electrode, this cathode active material is the composite oxides of lithium and transition elements, represents by following general formula (I) or (II):
Li xM yN 1-yO 2 (I)
M represents one or both elements among Ni, Co, Mn, Fe, Cu or the Cr,
N represents Ni, Co, Mn, Fe, Cr, Zn or Cu,
0＜x≤1.3 0≤y≤0.5
Li 1-x′M′ y′N′ 2-y′O 4 (II)
M ' represents Fe, Cu, Co, Zn, Ni or Cr,
N ' mainly represents Mn,
0＜x′≤1.0 0≤y′≤1；
(2) make anode with magnesium, nickel or zinc metal sheet;
(3) separate with the band alkaline-resisting material of micropore such as polyester, rubber membrane between the negative electrode anode;
(4) the electrolyte solution lithium hydroxide aqueous solution of 4-5 mol.
CN93108612A 1993-07-10 1993-07-10 Secondary battery with lithium ion aqueous solution Expired - Fee Related CN1059757C (en)

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CN1059757C true CN1059757C (en) 2000-12-20

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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1063582C (en) * 1996-11-26 2001-03-21 厦门大学 Method for manufacturing positive electrode of manganese series battery
CN1061474C (en) * 1996-12-25 2001-01-31 中国科学院化学研究所 Lithium ion battery and manufacture thereof
JP4137635B2 (en) 2000-11-16 2008-08-20 日立マクセル株式会社 Positive electrode active material and non-aqueous secondary battery
CN100426567C (en) * 2003-10-23 2008-10-15 肇庆市风华锂电池有限公司 Lithium ion cell positive pole material and producing method thereof
KR100789081B1 (en) 2003-11-17 2007-12-26 마쯔시다덴기산교 가부시키가이샤 Non-aqueous electrolyte secondary cell
JP2010541165A (en) * 2007-09-28 2010-12-24 スリーエム イノベイティブ プロパティズ カンパニー Sintered cathode composition
WO2011079482A1 (en) * 2009-12-29 2011-07-07 万向电动汽车有限公司 Battery
KR101758967B1 (en) * 2011-06-03 2017-07-17 포시텍 파워 툴스(소주) 컴퍼니. 리미티드. Battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS622458A (en) * 1985-04-19 1987-01-08 Mitsubishi Electric Corp Composite structured body for carbonate fuel cell
JPH0567467A (en) * 1991-09-09 1993-03-19 Asahi Chem Ind Co Ltd Nonaqueous secondary battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS622458A (en) * 1985-04-19 1987-01-08 Mitsubishi Electric Corp Composite structured body for carbonate fuel cell
JPH0567467A (en) * 1991-09-09 1993-03-19 Asahi Chem Ind Co Ltd Nonaqueous secondary battery

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