CN104779369A - Preparation method for positive electrode material of lithium ion battery, positive electrode material and battery - Google Patents
Preparation method for positive electrode material of lithium ion battery, positive electrode material and battery Download PDFInfo
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- CN104779369A CN104779369A CN201410016721.1A CN201410016721A CN104779369A CN 104779369 A CN104779369 A CN 104779369A CN 201410016721 A CN201410016721 A CN 201410016721A CN 104779369 A CN104779369 A CN 104779369A
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- lithium
- anode material
- ion batteries
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title abstract 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 238000005189 flocculation Methods 0.000 claims abstract description 10
- 230000016615 flocculation Effects 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 57
- 239000010405 anode material Substances 0.000 claims description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 9
- 229940051250 hexylene glycol Drugs 0.000 claims description 8
- 239000008236 heating water Substances 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 238000005303 weighing Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 238000011056 performance test Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ethyl carbonate ester Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method for a positive electrode material of a lithium ion battery, the positive electrode material and the battery; the method comprises the following steps: (1) according to the coefficient ratio of corresponding metal elements in a molecular formula of Li[Li(1/3-x/3)CoxMn(2/3-2x/3)]O2, respectively weighing a lithium-containing compound, a cobalt-containing compound and a manganese-containing compound, and preparing a mixed solution, wherein x is 0.4-0.6; and (2) adding a flocculation agent with the molar ratio of the flocculation agent to metal cations in the mixed solution of (2:1) to (20:1), to obtain a gel material, drying, and then calcining in an oxygen-containing atmosphere. The method allows all the raw material components to achieve atomic-level uniform mixing in a sol-gel state, a generated sol-gel substance is dispersed uniformly, the calcining time is shortened, and the calcined product has uniform composition. The lithium ion battery prepared from the material obtained by the method has the advantages of high specific capacity and good power multiplying performance.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery
The preparation method of positive electrode, positive electrode and battery.
Background technology
The development of information technology and the progress of novel electron instrument and equipment, make the research and development of high-energy secondary battery become heat subject.LiCoO
2as being widely used in most business-like positive electrode at present, being also the positive electrode that research is the most deep at present, there is the advantages such as operating voltage is high, electric discharge is steady, good cycle, but cobalt resource being rare, price is high, and having pollution to environment.The LiMn of spinel structure
2o
4there is the features such as higher operating voltage, cheap, environmental friendliness, but under lower Reversible Cycle capacity and high temperature, the rapid decay of capacity is one of key factor hindering its commercial applications.The LiFePO of relative low price
4electronic conductivity is poor, and actual discharge specific capacity only has 160mAh/g, and lower specific discharge capacity can not meet the demand of 3G electronic product to high power capacity.
Lithium-enriched cathodic material of lithium ion battery receives with its high power capacity and stable cycle performance and pays close attention to widely in recent years.Lithium-rich anode material is Li mainly
2mnO
3with stratified material LiMO
2the solid solution that (M=Ni, Co, Mn) is formed.Lithium-enriched cathodic material of lithium ion battery Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2li
2mnO
3with LiCoO
2by the solid solution that different proportion is formed, also as Co can be regarded
3+part replaces Li [Li
1/3mn
2/3] O
2or Li
2mnO
3in Li
+and Mn
4+.But lithium-rich anode material still exists in first charge-discharge process and has larger irreversible capacity loss namely coulombic efficiency is low first, and the problem such as high rate performance is poor, cycle performance is poor, limit its commercial applications.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of preparation method of anode material for lithium-ion batteries, positive electrode and battery are provided, the method makes each raw material components achieve the Homogeneous phase mixing of atomic level in sol-gel state, the sol-gel shape material generated is uniformly dispersed, shorten its calcination time, and firing product lithium-rich anode material uniform component.The specific capacity of the lithium ion battery that the material that the method obtains is made is high, good rate capability.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of preparation method of anode material for lithium-ion batteries, comprises the following steps:
(1) according to molecular formula Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2in the coefficient proportioning of respective metal element, take the compound containing lithium, the compound containing cobalt respectively, be configured to mixed solution containing the compound of manganese, wherein, x=0.4 ~ 0.6;
(2) in the described mixed solution in described step (1), flocculation agent is added, the mol ratio of the metal cation in the mixed solution in described flocculation agent and described step (1) is (2:1) ~ (20:1), obtain spawn, carry out calcination under an oxygen-containing atmosphere again by after this spawn drying, obtain anode material for lithium-ion batteries Li [Li
(1/3- x/3)co
xmn
(2/3-2x/3)] O
2.
Preferably, described flocculation agent is the mixture of multi-hydroxy compound and citric acid.
Preferably, the mol ratio of described multi-hydroxy compound and described citric acid is (2:1) ~ (10:1).
Preferably, described multi-hydroxy compound is any one or a few in ethylene glycol, glycerol, hexylene glycol, pentanediol.
Preferably, the described compound containing cobalt is any one or a few in cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride;
The described compound containing manganese is any one or a few in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride;
The described compound containing lithium is any one or a few in lithium nitrate, lithium carbonate, lithium hydroxide, lithium acetate.
Preferably, after adding flocculation agent, carry out heating water bath, obtain spawn in described step (2) in the described mixed solution in described step (1), the temperature of described water-bath is 50 DEG C ~ 90 DEG C.
Preferably, the calcination temperature in described step (2) is 350 DEG C ~ 700 DEG C, and calcination time is 5 hours ~ 60 hours.
Preferably, the concrete calcination process of described step (2) is: be first warmed up to 350 DEG C ~ 600 DEG C with the speed of 0.5 DEG C/min ~ 10 DEG C/min, and heat preservation sintering 1 hour ~ 12 hours;
Then be warmed up to 700 DEG C ~ 1000 DEG C with the speed of 1 DEG C/min ~ 10 DEG C/min, and be incubated calcining 2 hours ~ 24 hours;
Cool to 500 DEG C ~ 700 DEG C with the speed of 1 DEG C/min ~ 10 DEG C/min again, anneal 2 hours ~ 24 hours.
The present invention also provides a kind of anode material for lithium-ion batteries, and it is prepared by above-mentioned preparation method.
The present invention also provides a kind of lithium ion battery, and its positive pole comprises above-mentioned anode material for lithium-ion batteries.
The preparation method of the anode material for lithium-ion batteries in the present invention is that a kind of softening method prepares lithium-rich anode material Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2i.e. sol-gel process, prepare lithium-enriched cathodic material of lithium ion battery with traditional solid sintering technology and chemical precipitation method to compare, method of the present invention makes each raw material components under sol-gel state, achieve the Homogeneous phase mixing of atomic level, thus the sol-gel shape material generated is uniformly dispersed, substantially reduce the calcination time for sol-gel shape material, and the product lithium-rich anode material Li [Li that calcination is generated
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2uniform component, the consistency of product is good.The specific capacity of the lithium ion battery that the lithium-rich anode material using the method to obtain is made is high, good rate capability.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of preparation method of anode material for lithium-ion batteries, comprises the following steps:
(1) according to the molecular formula Li [Li of lithium-rich anode material
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2in the coefficient proportioning (wherein, x=0.4) of respective metal element, take lithium nitrate respectively, cobalt nitrate, manganese nitrate be configured to mixed solution, in mixed solution, the total concentration of metal cation is 2M.
(2) by the mixed solution strong agitation in step (1), and drip the mixed solution of ethylene glycol and citric acid wherein, wherein, the mol ratio of ethylene glycol and citric acid is 2:1, and the mol ratio of the metal cation in the mixed solution in the total mole number of ethylene glycol and citric acid and step (1) is 10:1.While dripping while stirring, carry out heating water bath, the temperature of water-bath is 50 DEG C, occurs red spawn, after this spawn is filtered, at the vacuum drying chamber inner drying 12 hours of 150 DEG C, obtain drying and show slightly fluffy block presoma, after grinding, obtaining precursor powder.By this precursor powder under oxygen atmosphere, be first warmed up to 500 DEG C with the speed of 3 DEG C/min, and heat preservation sintering 8 hours; Then be warmed up to 950 DEG C with the speed of 5 DEG C/min, and be incubated calcining 18 hours; Cool to 500 DEG C with the speed of 5 DEG C/min again, anneal 12 hours, obtain anode material for lithium-ion batteries Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2(wherein, x=0.4).
By this anode material for lithium-ion batteries and conductive agent acetylene black, binding agent PVDF(Kynoar) mix according to mass ratio 8: 1: 1, use NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on aluminium foil, put into baking oven, dry 1 hour at 80 ~ 120 DEG C, take out and be washed into pole piece, 85 DEG C of vacuumize 12 hours, carry out compressing tablet, 85 DEG C of vacuumize 12 hours, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is the LiPF of 1.5mol/L
6eC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1: 1) solution, barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
High rate performance test is carried out to this button cell: discharge and recharge is 0.01 ~ 1.5V by voltage, and charging and discharging currents is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, each circulation 5 times, wherein, 1C=700mA/g.High rate performance test result shows, under the condition of 0.1C, the specific discharge capacity of battery is 209.3mAh/g; Under the condition of 0.2C, the specific discharge capacity of battery is 191.8mAh/g; Under the condition of 0.5C, the specific discharge capacity of battery is 185.4mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 166.4mAh/g; The high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its positive pole comprises above-mentioned anode material for lithium-ion batteries.
The preparation method of the anode material for lithium-ion batteries in this embodiment is that a kind of softening method prepares lithium-rich anode material Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2i.e. sol-gel process, prepare lithium-enriched cathodic material of lithium ion battery with traditional solid sintering technology and chemical precipitation method to compare, the method of the present embodiment makes each raw material components under sol-gel state, achieve the Homogeneous phase mixing of atomic level, thus the sol-gel shape material generated is uniformly dispersed, substantially reduce the calcination time for sol-gel shape material, and the product lithium-rich anode material Li [Li that calcination is generated
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2uniform component, the consistency of product is good.The specific capacity of the lithium ion battery that the lithium-rich anode material using the method to obtain is made is high, good rate capability.
Embodiment 2
The present embodiment provides a kind of preparation method of anode material for lithium-ion batteries, comprises the following steps:
(1) according to the molecular formula Li [Li of lithium-rich anode material
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2in the coefficient proportioning (wherein, x=0.5) of respective metal element, take lithium carbonate, cobaltous sulfate, manganese sulfate and manganese chloride respectively and be configured to mixed solution, in mixed solution, the total concentration of metal cation is 1M.
(2) by the mixed solution strong agitation in step (1), and drip the mixed solution of hexylene glycol and citric acid wherein, wherein, the mol ratio of hexylene glycol and citric acid is 6:1, and the mol ratio of the metal cation in the mixed solution in the total mole number of hexylene glycol and citric acid and step (1) is 6:1.While dripping while stirring, carry out heating water bath, the temperature of water-bath is 90 DEG C, occurs red spawn, after this spawn is filtered, at the vacuum drying chamber inner drying 24 hours of 120 DEG C, obtain drying and show slightly fluffy block presoma, after grinding, obtaining precursor powder.By this precursor powder in air atmosphere, be first warmed up to 600 DEG C with the speed of 2 DEG C/min, and heat preservation sintering 12 hours; Then be warmed up to 1000 DEG C with the speed of 1 DEG C/min, and be incubated calcining 12 hours; Cool to 600 DEG C with the speed of 5 DEG C/min again, anneal 6 hours, obtain anode material for lithium-ion batteries Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2(wherein, x=0.5).
According to the method preparing button cell in embodiment 1, the obtained anode material for lithium-ion batteries of the present embodiment is used to make button cell, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, each circulation 5 times, wherein, 1C=700mA/g.High rate performance test result shows, under the condition of 0.1C, the specific discharge capacity of battery is 215.2mAh/g; Under the condition of 0.2C, the specific discharge capacity of battery is 183.1mAh/g; Under the condition of 0.5C, the specific discharge capacity of battery is 172.0mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 145.3mAh/g; The high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its positive pole comprises above-mentioned anode material for lithium-ion batteries.
Embodiment 3
The present embodiment provides a kind of preparation method of anode material for lithium-ion batteries, comprises the following steps:
(1) according to the molecular formula Li [Li of lithium-rich anode material
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2in the coefficient proportioning (wherein, x=0.6) of respective metal element, take lithium hydroxide respectively, cobalt chloride, cobalt nitrate, manganese chloride be configured to mixed solution, in mixed solution, the total concentration of metal cation is 2M.
(2) by the mixed solution strong agitation in step (1), and drip the mixed solution of glycerol and citric acid wherein, wherein, the mol ratio of glycerol and citric acid is 4:1, and the mol ratio of the metal cation in the mixed solution in the total mole number of glycerol and citric acid and step (1) is 2:1.While dripping while stirring, carry out heating water bath, the temperature of water-bath is 60 DEG C, occurs red spawn, after this spawn is filtered, at the vacuum drying chamber inner drying 24 hours of 175 DEG C, obtain drying and show slightly fluffy block presoma, after grinding, obtaining precursor powder.By this precursor powder in air atmosphere, be first warmed up to 500 DEG C with the speed of 5 DEG C/min, and heat preservation sintering 12 hours; Then be warmed up to 1000 DEG C with the speed of 1 DEG C/min, and be incubated calcining 12 hours; Cool to 600 DEG C with the speed of 5 DEG C/min again, anneal 6 hours, obtain anode material for lithium-ion batteries Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2(wherein, x=0.6).
According to the method preparing button cell in embodiment 1, the obtained anode material for lithium-ion batteries of the present embodiment is used to make button cell, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, each circulation 5 times, wherein, 1C=700mA/g.High rate performance test result shows, under the condition of 0.1C, the specific discharge capacity of battery is 223.7mAh/g; Under the condition of 0.2C, the specific discharge capacity of battery is 174.0mAh/g; Under the condition of 0.5C, the specific discharge capacity of battery is 163.4mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 132.1mAh/g; The high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its positive pole comprises above-mentioned anode material for lithium-ion batteries.
Embodiment 4
The present embodiment provides a kind of preparation method of anode material for lithium-ion batteries, comprises the following steps:
(1) according to the molecular formula Li [Li of lithium-rich anode material
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2in the coefficient proportioning (wherein, x=0.5) of respective metal element, take lithium hydroxide respectively, lithium carbonate, cobaltous sulfate, manganese sulfate be configured to mixed solution, in mixed solution, the total concentration of metal cation is 2.5M.
(2) by the mixed solution strong agitation in step (1), and drip the mixed solution of pentanediol and citric acid wherein, wherein, the mol ratio of pentanediol and citric acid is 10:1, and the mol ratio of the metal cation in the mixed solution in the total mole number of pentanediol and citric acid and step (1) is 20:1.While dripping while stirring, carry out heating water bath, the temperature of water-bath is 70 DEG C, occurs red spawn, after this spawn is filtered, at the vacuum drying chamber inner drying 12 hours of 120 DEG C, obtain drying and show slightly fluffy block presoma, after grinding, obtaining precursor powder.By this precursor powder under oxygen atmosphere, be first warmed up to 350 DEG C with the speed of 0.5 DEG C/min, and heat preservation sintering 6 hours; Then be warmed up to 700 DEG C with the speed of 10 DEG C/min, and be incubated calcining 24 hours; Cool to 500 DEG C with the speed of 10 DEG C/min again, anneal 2 hours, obtain anode material for lithium-ion batteries Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2(wherein, x=0.5).
The present embodiment provides a kind of lithium ion battery, and its positive pole comprises above-mentioned anode material for lithium-ion batteries.
Embodiment 5
The present embodiment provides a kind of preparation method of anode material for lithium-ion batteries, comprises the following steps:
(1) according to the molecular formula Li [Li of lithium-rich anode material
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2in the coefficient proportioning (wherein, x=0.4) of respective metal element, take lithium acetate respectively, cobalt acetate, manganese acetate be configured to mixed solution, in mixed solution, the total concentration of metal cation is 3M.
(2) by the mixed solution strong agitation in step (1), and drip the mixed solution of ethylene glycol, hexylene glycol and citric acid wherein, wherein, the amount of substance of ethylene glycol and hexylene glycol and be 5:1 with the mol ratio of citric acid, the mol ratio of the metal cation in the mixed solution in the total mole number of ethylene glycol, hexylene glycol and citric acid and step (1) is 15:1.While dripping while stirring, carry out heating water bath, the temperature of water-bath is 80 DEG C, occurs red spawn, after this spawn is filtered, at the vacuum drying chamber inner drying 10 hours of 150 DEG C, obtain drying and show slightly fluffy block presoma, after grinding, obtaining precursor powder.By this precursor powder in air atmosphere, be first warmed up to 400 DEG C with the speed of 10 DEG C/min, and heat preservation sintering 1 hour; Then be warmed up to 800 DEG C with the speed of 7 DEG C/min, and be incubated calcining 2 hours; Cool to 700 DEG C with the speed of 1 DEG C/min again, anneal 24 hours, obtain anode material for lithium-ion batteries Li [Li
(1/3- x/3)co
xmn
(2/3-2x/3)] O
2(wherein, x=0.4).
The present embodiment provides a kind of lithium ion battery, and its positive pole comprises above-mentioned anode material for lithium-ion batteries.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for anode material for lithium-ion batteries, is characterized in that, comprises the following steps:
(1) according to molecular formula Li [Li
(1/3-x/3)co
xmn
(2/3-2x/3)] O
2in the coefficient proportioning of respective metal element, take the compound containing lithium, the compound containing cobalt respectively, be configured to mixed solution containing the compound of manganese, wherein, x=0.4 ~ 0.6;
(2) in the described mixed solution in described step (1), flocculation agent is added, the mol ratio of the metal cation in the mixed solution in described flocculation agent and described step (1) is (2:1) ~ (20:1), obtain spawn, carry out calcination under an oxygen-containing atmosphere again by after this spawn drying, obtain anode material for lithium-ion batteries Li [Li
(1/3- x/3)co
xmn
(2/3-2x/3)] O
2.
2. the preparation method of anode material for lithium-ion batteries according to claim 1, is characterized in that, described flocculation agent is the mixture of multi-hydroxy compound and citric acid.
3. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, the mol ratio of described multi-hydroxy compound and described citric acid is (2:1) ~ (10:1).
4. the preparation method of anode material for lithium-ion batteries according to claim 2, is characterized in that, described multi-hydroxy compound is any one or a few in ethylene glycol, glycerol, hexylene glycol, pentanediol.
5. the preparation method of anode material for lithium-ion batteries according to claim 1, is characterized in that, the described compound containing cobalt is any one or a few in cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride;
The described compound containing manganese is any one or a few in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride;
The described compound containing lithium is any one or a few in lithium nitrate, lithium carbonate, lithium hydroxide, lithium acetate.
6. the preparation method of anode material for lithium-ion batteries according to claim 1, it is characterized in that, after adding flocculation agent in described step (2) in the described mixed solution in described step (1), carry out heating water bath, obtain spawn, the temperature of described water-bath is 50 DEG C ~ 90 DEG C.
7. the preparation method of anode material for lithium-ion batteries according to claim 1, is characterized in that, the calcination temperature in described step (2) is 350 DEG C ~ 700 DEG C, and calcination time is 5 hours ~ 60 hours.
8. the preparation method of anode material for lithium-ion batteries according to claim 7, it is characterized in that, the concrete calcination process of described step (2) is: be first warmed up to 350 DEG C ~ 600 DEG C with the speed of 0.5 DEG C/min ~ 10 DEG C/min, and heat preservation sintering 1 hour ~ 12 hours;
Then be warmed up to 700 DEG C ~ 1000 DEG C with the speed of 1 DEG C/min ~ 10 DEG C/min, and be incubated calcining 2 hours ~ 24 hours;
Cool to 500 DEG C ~ 700 DEG C with the speed of 1 DEG C/min ~ 10 DEG C/min again, anneal 2 hours ~ 24 hours.
9. an anode material for lithium-ion batteries, is characterized in that, it is for being prepared by the preparation method described in claim 1 ~ 8 any one.
10. a lithium ion battery, is characterized in that, its positive pole comprises the anode material for lithium-ion batteries that right is wanted described in 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099044A (en) * | 2016-06-29 | 2016-11-09 | 中国科学技术大学 | A kind of method that solution phase inversion prepares lithium ion cell positive |
| CN108461730A (en) * | 2018-03-14 | 2018-08-28 | 中南大学 | A kind of anode material for lithium-ion batteries and preparation method thereof |
-
2014
- 2014-01-14 CN CN201410016721.1A patent/CN104779369A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 赵煜娟等: "改性Pechini方法合成富锂正极材料Li[Li(1/3-x/3)CoxMn(2/3-2x/3)]O2及性能研究", 《化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106099044A (en) * | 2016-06-29 | 2016-11-09 | 中国科学技术大学 | A kind of method that solution phase inversion prepares lithium ion cell positive |
| CN108461730A (en) * | 2018-03-14 | 2018-08-28 | 中南大学 | A kind of anode material for lithium-ion batteries and preparation method thereof |
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Application publication date: 20150715 |