CN102664255A - Lithium nickel manganese oxide material and preparation method thereof and lithium ion battery containing lithium nickel manganese oxide material - Google Patents
Lithium nickel manganese oxide material and preparation method thereof and lithium ion battery containing lithium nickel manganese oxide material Download PDFInfo
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- CN102664255A CN102664255A CN201210168897XA CN201210168897A CN102664255A CN 102664255 A CN102664255 A CN 102664255A CN 201210168897X A CN201210168897X A CN 201210168897XA CN 201210168897 A CN201210168897 A CN 201210168897A CN 102664255 A CN102664255 A CN 102664255A
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- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title abstract 10
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000010532 solid phase synthesis reaction Methods 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 139
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 28
- 229910012752 LiNi0.5Mn0.5O2 Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 239000008247 solid mixture Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229910006703 Li—Ni—Mn—O Inorganic materials 0.000 claims description 4
- 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
- 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
- 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 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 29
- 239000006104 solid solution Substances 0.000 description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011164 primary particle Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- -1 ethyl carbonate ester Chemical class 0.000 description 3
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001170 xLi2MnO3-(1−x)LiMO2 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 1
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 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
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Images
Classifications
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- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium nickel manganese oxide material and a preparation method thereof and a lithium ion battery containing the lithium nickel manganese oxide material, relates to the technical field of lithium ion batteries, and can solve the problems that the first coulomb efficiency or specific capacity of an existing lithium nickel manganese oxide material and a lithium ion battery prepared with the same is low and the cycle performance is poor. The lithium nickel manganese oxide material preparation method includes the following steps of precipitation to prepare a nickel manganese precursor, pretreatment of the precursor and solid phase synthesis. Proper process parameters are selected to obtain the lithium nickel manganese oxide material with good performance, so that the first coulomb efficiency, specific capacity and cycle performance of the lithium nickel manganese oxide material and the lithium ion battery prepared with the same are high. The lithium nickel manganese oxide material is prepared by the preparation method. The lithium ion battery comprises the lithium nickel manganese oxide material.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of Li-Ni-Mn-O material and preparation method thereof, contain the lithium ion battery of this material.
Background technology
Microelectronics and correlation technique have obtained developing rapidly in recent years, and modern society requires for example LiCoO of increasingly high, general positive electrode to aspects such as the energy density of lithium ion battery, volume, cycle life, fail safe
2, LiMn
2O
4, LiFePO
4, ternary material etc. more and more can not satisfy the demand of high power capacity, high-energy-density energy storage device, stratiform lithium-rich anode material xLi
2MnO
3(1-x) LiMO
2(M=Mn, Ni, Co, Ni
0.5Mn
0.5, Cr, Ni
1/3Co
1/3Mn
1/3, Fe ...) be a kind of α-NaFeO
2The type solid-solution material is by the Li of stratiform
2MnO
3And LiMO
2(M=Mn, Ni, Co, Ni
0.5Mn
0.5, Fe ...) form, (200 ~ 300mAh/g) become the focus of people's research with its distinctive height ratio capacity.Bibliographical information aLiNi is arranged
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(a=0,0.1,0.15; 0.2,0.3,0.4) and material discharges and recharges with the electric current of 15mA/g at 2 ~ 4.95V; First discharge specific capacity is 200 ~ 260mAh/g, but its cyclical stability is relatively poor, and circulating, specific discharge capacity has reduced by 40 ~ 60mAh/g after 30 times; When with big electric current (for example 1C) when discharging and recharging, the specific capacity decay is faster, and cyclical stability is poor; And its coulombic efficiency is low first, be 60% ~ 70%.In sum, the aLiNi for preparing at present
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Therefore (a=0,0.1,0.15,0.2,0.3,0.4) material property does not satisfy requirement of actual application, presses for to make improvements and optimize, and makes it to have good performance, and realizes the suitability for industrialized production of this material.
Summary of the invention
The objective of the invention is to solve the aLiNi of prior art
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(a=0,0.1,0.15,0.2,0.3,0.4) material and low or specific capacity is low, the problem of cycle performance difference by the efficient of enclosed pasture first of the lithium ion battery of its preparation provides a kind of aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(0.6≤a≤0.7) material.
Solving the technical scheme that technical problem of the present invention adopted is a kind of aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(0.6≤a≤0.7) material.
ALiNi provided by the invention
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(0.6≤a≤0.7) material is by spinel-type LiNi
0.5Mn
1..5O
4, stratiform Li
2MnO
3, stratiform LiNi
0.5Mn
0.5O
2The solid-solution material that forms together has height ratio capacity, good cycling stability, multiplying power property, coulombic efficiency advantages of higher first preferably, has both had lithium-rich anode material xLi
2MnO
3(1-x) LiMO
2High capacity characteristics, have the high rate capability of spinelle Li-Ni-Mn-O positive electrode, high, the good cycling stability of coulombic efficiency first again.
The problem that the present invention will solve also comprises, to the aLiNi of prior art for preparing
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(a=0,0.1,0.15,0.2,0.3,0.4) material and low or specific capacity is low, the problem of cycle performance difference by the efficient of enclosed pasture first of the lithium ion battery of its preparation provides a kind of aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(0.6≤a≤0.7) preparation methods.
The technical scheme that solution the invention described above technical problem is adopted is a kind of aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods, wherein: 0.6≤a≤0.7 comprises the steps:
1) prepared by co-precipitation nickel manganese presoma step
In amount of substance ratio Ni: Mn=1: the mixture aqueous solution of 3 preparation nickel presomas and manganese presoma, in mixture aqueous solution, add precipitation reagent, make Ni
2+, Mn
2+Deposition obtains nickel manganese presoma;
2) pre-treatment step of nickel manganese presoma, it comprises in following two kinds of processes any one:
In amount of substance ratio Li: Ni: Mn=(3.264～3.78): lithium source and nickel manganese presoma batch mixing got solid mixture in 1: 3, pulverize, obtain crushed mixture; Under oxygen-containing atmosphere, be heated to 400 ~ 600 ℃ with the programming rate of 0.5 ~ 10 ℃/min, heat preservation sintering 2 ~ 12h, pretreated nickel manganese presoma; Or
With nickel manganese presoma under oxygen-containing atmosphere; Programming rate with 0.5 ~ 10 ℃/min is heated to 400 ~ 600 ℃; Heat preservation sintering 2 ~ 12h obtains Ni, Mn oxide, then in amount of substance ratio Li: Ni: Mn=(3.264～3.78): lithium source and said Ni, Mn oxide batch mixing got solid mixture in 1: 3; Pulverize, obtain pretreated nickel manganese presoma;
3) solid phase synthesis step:
With step 2) the pretreated nickel manganese presoma of gained under oxygen-containing atmosphere, be heated to 800 ~ 950 ℃ with the programming rate of 0.5 ~ 10 ℃/min, calcining 2 ~ 24h is cooled to room temperature naturally, promptly obtains aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(0.6≤a≤0.7) material.
Preferably, said oxygen-containing atmosphere is air atmosphere or pure oxygen atmosphere.
Preferably, described pulverizing is ball mill grinding or grinds.
Further preferably, described ball mill grinding is a wet ball grinding, and said wet ball grinding comprises: with ethanol and the solid mixture mixed by (1 ~ 1.3): 1mL/g, with rotating speed ball milling 2 ~ 16h of 300 ~ 650r/min.
Preferably, described nickel presoma is one or more in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride.
Preferably, described manganese presoma is one or more in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride.
Preferably, described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, the lithia.
Preferably, described precipitation reagent is Na
2CO
3Solution, K
2CO
3Solution, (NH
4)
2CO
3Solution, NaHCO
3Solution, KHCO
3Solution, NH
4HCO
3In the solution one or more.
The present invention is through choosing the aLiNi that appropriate parameters has obtained function admirable
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(0.6≤a≤0.7) material, thus make this material and high by the efficient of enclosed pasture first of the lithium ion battery of its preparation, specific capacity is high and cycle performance is good, and the preparation technology of this material is simple, is easy to suitability for industrialized production.
Technical problem to be solved by this invention also comprises, to existing by aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Enclosed pasture efficient is low or specific capacity is low, the problem of cycle performance difference first for the lithium ion battery of (a=0,0.1,0.15,0.2,0.3,0.4) material preparation, and the lithium ion battery that a kind of efficient of enclosed pasture first is high, specific capacity is high and cycle performance is good is provided.
Solving the technical scheme that technical problem of the present invention adopted is a kind of lithium ion battery, and its positive pole contains above-mentioned aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(0.6≤a≤0.7) material.
Because the positive pole of lithium ion battery of the present invention contains above-mentioned aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2(0.6≤a≤0.7) material,
So enclosed pasture efficient is high first, specific capacity is high and cycle performance is good for it.
Description of drawings
Fig. 1 is ESEM (SEM) figure of the prepared solid solution positive electrode of the embodiment of the invention 1.
Fig. 2 is the discharge cycles performance curve of the prepared solid solution positive electrode of the embodiment of the invention 1.
Fig. 3 is the prepared discharge cycles performance curve of solid solution positive electrode under different charge-discharge magnifications of the embodiment of the invention 1.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with accompanying drawing and embodiment.
Embodiment 1
Present embodiment provides a kind of 0.62LiNi
0.5Mn
1.5O
40.38Li
2MnO
30.38LiNi
0.5Mn
0.5O
2Preparation methods comprises:
Step 1. prepared by co-precipitation presoma
In amount of substance ratio Ni: Mn=1: the mixture aqueous solution of 3 preparation nickel acetates and manganese nitrate under stirring, is the Na of 0.5M to the mixed solution and dripping molar concentration
2CO
3Solution makes Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain presoma nickel manganese compound carbonate.
The preliminary treatment of step 2. nickel manganese presoma
In amount of substance ratio Li: Ni: Mn=3.463: presoma nickel manganese compound carbonate batch mixing got solid mixture with lithium nitrate and lithium carbonate (both amount of substance ratios are 1: 1) in 1: 3, and wherein the volatile quantity of Li in processing procedure is 4.3%; And be that 1.2mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 13h of 400r/min, crushed mixture.Crushed mixture is taken out dry, then under pure oxygen atmosphere, is heated to 400 ℃ with the programming rate of 0.5 ℃/min, heat preservation sintering 5h, pretreated nickel manganese presoma.
Step 3. solid phase synthesis
Under air atmosphere, the pretreated nickel manganese presoma of step 2 gained is heated to 800 ℃, calcining 2h with the programming rate of 10 ℃/min; At last be cooled to room temperature naturally, promptly obtain 0.62LiNi
0.5Mn
1.5O
40.38Li
2MnO
30.38LiNi
0.5Mn
0.5O
2Material.
Optional, can continue with prepared 0.62LiNi
0.5Mn
1.5O
40.38Li
2MnO
30.38LiNi
0.5Mn
0.5O
2The material preparation Experimental cell is with pole piece and test battery.
The preparation experiment battery uses the process of pole piece to be: with 0.62LiNi
0.5Mn
1.5O
40.38Li
2MnO
30.38LiNi
0.5Mn
0.5O
2Positive electrode and conductive agent acetylene black, binding agent PVDF (Kynoar) mix according to mass ratio at 8: 1: 1, with NMP (1-Methyl-2-Pyrrolidone) this mixture are modulated into slurry, evenly are coated on the aluminium foil; Put into baking oven, dry 1h down, take out and be washed into pole piece at 80 ℃; At 85 ℃ of following vacuumize 12h; Carry out compressing tablet,, make Experimental cell and use pole piece at 85 ℃ of following vacuumize 12h.
The process of preparation test battery is: the pole piece with above-mentioned preparation is a positive pole; With the lithium sheet is to electrode; Electrolyte is that concentration is the solution of the LiPF6 of 1.5mol/L, and its solvent is EC (ethyl carbonate ester)+DMC (dimethyl carbonate), and wherein the volume ratio of EC (ethyl carbonate ester) and DMC (dimethyl carbonate) is 1: 1; Barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.Test battery is carried out the discharge cycles test, and its charge and discharge cycles is set to: the 1st ~ 5 charging and discharging currents is 0.1C, and the 6th ~ 80 time charging and discharging currents is 0.2C; And to test battery being carried out the high rate performance test, its test process is: charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C (1C=220mA/g), each multiplying power circulation 5 times; Wherein, its to discharge and recharge by voltage be 2.0 ~ 4.8V.
As shown in Figure 1, the 0.62LiNi of present embodiment preparation
0.5Mn
1.5O
40.38Li
2MnO
30.38LiNi
0.5Mn
0.5O
2The SEM test result of material shows that product is spinelle, stratiform mixed type solid solution, even particle size, and primary particle size is 0.4 ~ 0.6um, fewer particle generation agglomeration.
The 0.62LiNi of present embodiment preparation
0.5Mn
1.5O
40.38Li
2MnO
30.38LiNi
0.5Mn
0.5O
2The discharge cycles test data of material is seen table 1, and the enclosed pasture efficient of visible this material is higher, and 80 times circulation back specific discharge capacity keeps better.
As shown in Figure 2, the 0.62LiNi of present embodiment preparation
0.5Mn
1.5O
40.38Li
2MnO
30.38LiNi
0.5Mn
0.5O
2The material discharging cycle performance is good.
As shown in Figure 3, the 0.62LiNi of present embodiment preparation
0.5Mn
1.5O
40.38Li
2MnO
30.38LiNi
0.5Mn
0.5O
2The material cycle performance that under different charge-discharge magnifications, discharges is good.
Embodiment 2
Present embodiment provides a kind of 0.6LiNi
0.5Mn
1.5O
40.4Li
2MnO
30.4LiNi
0.5Mn
0.5O
2Preparation methods:
Step 1. prepared by co-precipitation nickel manganese presoma
In amount of substance ratio Ni: Mn=1: 3 preparation nickel nitrate and nickel acetates (both amount of substance ratios are 1: 1), the mixture aqueous solution of manganese sulfate under stirring, is the K of 0.3M to the mixed solution and dripping molar concentration
2CO
3Solution makes Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain presoma nickel manganese compound carbonate.
The preliminary treatment of step 2. nickel manganese presoma
Drying with step 1) gained presoma nickel manganese compound carbonate; Sintering under air atmosphere; Programming rate with 10 ℃/min is heated to 600 ℃; Heat preservation sintering 2h obtains Ni, Mn oxide, then in amount of substance ratio Li: Ni: Mn=3.78: lithium carbonate and this Ni, Mn oxide batch mixing got solid mixture in 1: 3; And be that 1mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 10h of 500r/min, crushed mixture.
Step 3. solid phase synthesis
The crushed mixture that step 2 is obtained takes out dry, and sintering under pure oxygen atmosphere then is heated to 950 ℃, calcining 12h with the programming rate of 0.5 ℃/min; At last be cooled to room temperature naturally, wherein the volatile quantity of Li in processing procedure is 5%, promptly obtains 0.6LiNi
0.5Mn
1.5O
40.4Li
2MnO
30.4LiNi
0.5Mn
0.5O
2Material.
Optional, can continue with prepared 0.6LiNi
0.5Mn
1.5O
40.4Li
2MnO
30.4LiNi
0.5Mn
0.5O
2The material preparation Experimental cell is with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The 0.6LiNi of present embodiment preparation
0.5Mn
1.5O
40.4Li
2MnO
30.4LiNi
0.5Mn
0.5O
2The SEM test result of material shows that product is spinelle, stratiform mixed type solid solution, even particle size, and primary particle size is 0.4 ~ 0.5um, fewer particle generation agglomeration.
The 0.6LiNi of present embodiment preparation
0.5Mn
1.5O
40.4Li
2MnO
30.4LiNi
0.5Mn
0.5O
2The discharge cycles test data of material is seen table 1, and the enclosed pasture efficient of visible this material is higher, and 80 times circulation back specific discharge capacity keeps better.
Embodiment 3
Present embodiment provides a kind of 0.61LiNi
0.5Mn
1.5O
40.39Li
2MnO
30.39LiNi
0.5Mn
0.5O
2Preparation methods comprises:
Step 1. prepared by co-precipitation nickel manganese presoma
In amount of substance ratio Ni: Mn=1: 3 preparation nickelous sulfates, the mixture aqueous solution of manganese chloride and manganese sulfate (both amount of substance ratios are 1: 1) under stirring, is the NaHCO of 2M to the mixed solution and dripping molar concentration
3Solution makes Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain presoma nickel manganese compound carbonate.
The preliminary treatment of step 2. nickel manganese presoma
In amount of substance ratio Li: Ni: Mn=3.6312: lithium acetate and presoma nickel manganese compound carbonate batch mixing got solid mixture in 1: 3; And be that 1.3mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 16h of 300r/min, crushed mixture.Crushed mixture is taken out dry, then under air atmosphere, is heated to 550 ℃ with the programming rate of 4 ℃/min, heat preservation sintering 8h, pretreated nickel manganese presoma.
Step 3. solid phase synthesis
Under air atmosphere, the pretreated nickel manganese presoma of step 2 gained is heated to 850 ℃, calcining 24h with the programming rate of 6 ℃/min; At last be cooled to room temperature naturally, wherein the volatile quantity of Li in processing procedure is 2%, promptly obtains 0.61LiNi
0.5Mn
1.5O
40.39Li
2MnO
30.39LiNi
0.5Mn
0.5O
2Material.
Optional, can continue with prepared 0.61LiNi
0.5Mn
1.5O
40.39Li
2MnO
30.39LiNi
0.5Mn
0.5O
2The material preparation Experimental cell is with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The 0.61LiNi of present embodiment preparation
0.5Mn
1.5O
40.39Li
2MnO
30.39LiNi
0.5Mn
0.5O
2The SEM test result of material shows that product is spinelle, stratiform mixed type solid solution, even particle size, and primary particle size is 0.3 ~ 0.5um, fewer particle generation agglomeration.
The 0.61LiNi of present embodiment preparation
0.5Mn
1.5O
40.39Li
2MnO
30.39LiNi
0.5Mn
0.5O
2The discharge cycles test data of material is seen table 1, and the enclosed pasture efficient of visible this material is higher, and 80 times circulation back specific discharge capacity keeps better.
Embodiment 4
Present embodiment provides a kind of 0.68LiNi
0.5Mn
1.5O
40.32Li
2MnO
30.32LiNi
0.5Mn
0.5O
2Preparation methods:
Step 1. prepared by co-precipitation nickel manganese presoma
In amount of substance ratio Ni: Mn=1: the mixture aqueous solution of 3 preparation nickel acetates and manganese acetate under stirring, is that 2M is the (NH of 1M to the mixed solution and dripping molar concentration
4)
2CO
3Solution makes Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain presoma nickel manganese compound carbonate.
The preliminary treatment of step 2. nickel manganese presoma
Drying with step 1) gained presoma nickel manganese compound carbonate; Sintering under pure oxygen atmosphere; Programming rate with 1 ℃/min is heated to 500 ℃; Heat preservation sintering 12h obtains Ni, Mn oxide, then in amount of substance ratio Li: Ni: Mn=3.4112: lithium hydroxide and this Ni, Mn oxide batch mixing got solid mixture in 1: 3; And be that 1.3mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 2h of 600r/min, crushed mixture.
Step 3. solid phase synthesis
The crushed mixture that step 2 is obtained takes out dry, and sintering under pure oxygen atmosphere then is heated to 900 ℃, calcining 4h with the programming rate of 8 ℃/min; At last be cooled to room temperature naturally, wherein the volatile quantity of Li in processing procedure is 4%, promptly obtains 0.68LiNi
0.5Mn
1.5O
40.32Li
2MnO
30.32LiNi
0.5Mn
0.5O
2Material.
Optional, can continue with prepared 0.68LiNi
0.5Mn
1.5O
40.32Li
2MnO
30.32LiNi
0.5Mn
0.5O
2The material preparation Experimental cell is with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The 0.68LiNi of present embodiment preparation
0.5Mn
1.5O
40.32Li
2MnO
30.32LiNi
0.5Mn
0.5O
2The SEM test result of material shows that product is spinelle, stratiform mixed type solid solution, even particle size, and primary particle size is 0.5 ~ 0.7um, fewer particle generation agglomeration.
The 0.68LiNi of present embodiment preparation
0.5Mn
1.5O
40.32Li
2MnO
30.32LiNi
0.5Mn
0.5O
2The discharge cycles test data of material is seen table 1, and the enclosed pasture efficient of visible this material is higher, and 80 times circulation back specific discharge capacity keeps better.
Embodiment 5
Present embodiment provides a kind of 0.7LiNi
0.5Mn
1.5O
40.3Li
2MnO
30.3LiNi
0.5Mn
0.5O
2Preparation methods comprises:
Step 1. prepared by co-precipitation nickel manganese presoma
In amount of substance ratio Ni: Mn=1: the mixture aqueous solution of 3 preparation nickel chlorides and manganese nitrate under stirring, is the KHCO of 1.5M to the mixed solution and dripping molar concentration
3Solution makes Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain presoma nickel manganese compound carbonate.
The preliminary treatment of step 2. nickel manganese presoma
In amount of substance ratio Li: Ni: Mn=3.264: lithia and presoma nickel manganese compound carbonate batch mixing got solid mixture in 1: 3; And be that 1mL/g adds ball mill in the ratio of ethanol and solid mixture, with the rotating speed ball milling 7h of 650r/min, crushed mixture.Crushed mixture is taken out dry, then under air atmosphere, is heated to 400 ℃ with the programming rate of 7 ℃/min, heat preservation sintering 3h, pretreated nickel manganese presoma.
Step 3. solid phase synthesis
Under air atmosphere, the pretreated nickel manganese presoma of step 2 gained is heated to 880 ℃, calcining 18h with the programming rate of 4 ℃/min; At last be cooled to room temperature naturally, wherein the volatile quantity of Li in processing procedure is 2%, promptly obtains 0.7LiNi
0.5Mn
1.5O
40.3Li
2MnO
30.3LiNi
0.5Mn
0.5O
2Material.
Optional, can continue with prepared 0.7LiNi
0.5Mn
1.5O
40.3Li
2MnO
30.3LiNi
0.5Mn
0.5O
2The material preparation Experimental cell is with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The 0.7LiNi of present embodiment preparation
0.5Mn
1.5O
40.3Li
2MnO
30.3LiNi
0.5Mn
0.5O
2The SEM test result of material shows that product is spinelle, stratiform mixed type solid solution, even particle size, and primary particle size is 0.4 ~ 0.6um, fewer particle generation agglomeration.
The 0.7LiNi of present embodiment preparation
0.5Mn
1.5O
40.3Li
2MnO
30.3LiNi
0.5Mn
0.5O
2The discharge cycles test data of material is seen table 1, and the enclosed pasture efficient of visible this material is higher, and 80 times circulation back specific discharge capacity keeps better.
Embodiment 6
Present embodiment provides a kind of 0.65LiNi
0.5Mn
1.5O
40.35Li
2MnO
30.35LiNi
0.5Mn
0.5O
2Preparation methods:
Step 1. prepared by co-precipitation nickel manganese presoma
In amount of substance ratio Ni: Mn=1: the mixture aqueous solution of 3 preparation nickel nitrates and manganese chloride under stirring, is the NH of 2.2M to the mixed solution and dripping molar concentration
4HCO
3Solution and molar concentration are the NaHCO of 2M
3The mixed solution of solution (both amount of substance ratios are 1: 1) makes Ni
2+, Mn
2+Deposition fully, leave standstill 2h after, suction filtration, three times, 110 ℃ dry 12h of washing obtain presoma nickel manganese compound carbonate.
The preliminary treatment of step 2. nickel manganese presoma
With the drying of step 1) gained presoma nickel manganese compound carbonate, sintering under air atmosphere is heated to 400 ℃ with the programming rate of 2 ℃/min, and heat preservation sintering 10h obtains Ni, Mn oxide Ni
0.5Mn
1.5O
4, then in amount of substance ratio Li: Ni: Mn=3.57: lithium carbonate and this Ni, Mn oxide batch mixing got solid mixture in 1: 3; Grind crushed mixture.
Step 3. solid phase synthesis
The crushed mixture that step 2 is obtained takes out dry, and sintering under pure oxygen atmosphere then is heated to 930 ℃, calcining 8h with the programming rate of 2 ℃/min; At last be cooled to room temperature naturally, wherein the volatile quantity of Li in processing procedure is 5%, promptly obtains 0.65LiNi
0.5Mn
1.5O
40.35Li
2MnO
30.35LiNi
0.5Mn
0.5O
2Material.
Optional, can continue with prepared 0.65LiNi
0.5Mn
1.5O
40.35Li
2MnO
30.35LiNi
0.5Mn
0.5O
2The material preparation Experimental cell is with pole piece and test battery.
The preparation experiment battery is identical with method among the embodiment 1 with pole piece and test battery method.
The 0.65LiNi of present embodiment preparation
0.5Mn
1.5O
40.35Li
2MnO
30.35LiNi
0.5Mn
0.5O
2The SEM test result of material shows that product is spinelle, stratiform mixed type solid solution, even particle size, and primary particle size is 0.5 ~ 0.7um, fewer particle generation agglomeration.
The 0.65LiNi of present embodiment preparation
0.5Mn
1.5O
40.35Li
2MnO
30.35LiNi
0.5Mn
0.5O
2The discharge cycles test data of material is seen table 1, and the enclosed pasture efficient of visible this material is higher, and 80 times circulation back specific discharge capacity keeps better.
Solid-solution material discharge cycles test data that table 1 embodiment of the invention is prepared and coulombic efficiency tables of data first
Need to prove; Of above-mentioned each embodiment; In nickel manganese presoma nickel manganese compound carbonate pre-treatment step, can carry out sintering to nickel manganese presoma earlier and then mix with the lithium source, perhaps also can be earlier with nickel manganese presoma with carry out sintering again after mix in the lithium source; As long as guarantee nickel manganese presoma is carried out oversintering, these two kinds of methods are to finally obtaining aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2The character of material does not have the essence influence.
Obviously, the preparation method of above-mentioned each embodiment also can carry out many known variations; For example: other known compound also can be selected in nickel presoma, manganese presoma, lithium source; Pulverize also can adopt except that grind with ball mill grinding other known manner carry out; Ball mill grinding can be the wet-milling of use other ball milling agent except that ethanol; Precipitation reagent can be except that Na
2CO
3Solution, K
2CO
3Solution, (NH
4)
2CO
3Solution, NaHCO
3Solution, KHCO
3Solution, NH
4HCO
3Beyond the solution other can be realized the known reagent of the object of the invention.
Embodiment 7
Present embodiment provides a kind of solid-solution material by method for preparing.
Embodiment 8
The lithium ion battery that present embodiment provides a kind of positive pole to contain above-mentioned solid-solution material, this lithium ion battery for example also comprises other necessary assembly certainly, negative pole, barrier film, electrolyte and shell etc. repeat no more here.
It is understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.
Claims (10)
1. a Li-Ni-Mn-O material is characterized in that,
Its molecular formula is aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2, wherein: 0.6≤a≤0.7.
2. aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods, wherein: 0.6≤a≤0.7, it is characterized in that, comprise the steps:
1) prepared by co-precipitation nickel manganese presoma step
Mixture aqueous solution in amount of substance ratio Ni ︰ Mn=1 ︰ 3 preparation nickel presomas and manganese presoma adds precipitation reagent in mixture aqueous solution, make Ni
2+, Mn
2+Deposition obtains nickel manganese presoma;
2) pre-treatment step of nickel manganese presoma, it comprises in following two kinds of processes any one:
(3.264～3.78) ︰, 1 ︰ 3 gets solid mixture with lithium source and nickel manganese presoma batch mixing, pulverizes, and obtains crushed mixture in amount of substance ratio Li ︰ Ni ︰ Mn=; Under oxygen-containing atmosphere, be heated to 400 ~ 600 ℃ with the programming rate of 0.5 ~ 10 ℃/min, heat preservation sintering 2 ~ 12h, pretreated nickel manganese presoma; Or
With nickel manganese presoma under oxygen-containing atmosphere; Programming rate with 0.5 ~ 10 ℃/min is heated to 400 ~ 600 ℃; Heat preservation sintering 2 ~ 12h obtains Ni, Mn oxide, and (3.264～3.78) ︰, 1 ︰ 3 gets solid mixture with lithium source and said Ni, Mn oxide batch mixing in amount of substance ratio Li ︰ Ni ︰ Mn=then; Pulverize, obtain pretreated nickel manganese presoma;
3) solid phase synthesis step:
With step 2) the pretreated nickel manganese presoma of gained under oxygen-containing atmosphere, be heated to 800 ~ 950 ℃ with the programming rate of 0.5 ~ 10 ℃/min, calcining 2 ~ 24h is cooled to room temperature naturally, promptly obtains aLiNi
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Material.
3. aLiNi as claimed in claim 2
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods is characterized in that, said oxygen-containing atmosphere is air atmosphere or pure oxygen atmosphere.
4. aLiNi as claimed in claim 2
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods is characterized in that, described pulverizing is ball mill grinding or grinds.
5. aLiNi as claimed in claim 4
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods is characterized in that, described ball mill grinding is a wet ball grinding, and said wet ball grinding comprises: with ethanol and solid mixture by (mixed of 1 ~ 1.3) ︰ 1mL/g is with rotating speed ball milling 2 ~ 16h of 300 ~ 650r/min.
6. like any described aLiNi in the claim 1 to 5
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods is characterized in that, described nickel presoma is one or more in nickel nitrate, nickel acetate, nickelous sulfate, the nickel chloride.
7. like any described aLiNi in the claim 1 to 5
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods is characterized in that, described manganese presoma is one or more in manganese nitrate, manganese acetate, manganese sulfate, the manganese chloride.
8. like any described aLiNi in the claim 1 to 5
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods is characterized in that, described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate, the lithia.
9. like any described aLiNi in the claim 1 to 5
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Preparation methods is characterized in that, described precipitation reagent is Na
2CO
3Solution, K
2CO
3Solution, (NH
4)
2CO
3Solution, NaHCO
3Solution, KHCO
3Solution, NH
4HCO
3In the solution one or more.
10. a lithium ion battery is characterized in that, its positive pole contains the said aLiNi of claim 1
0.5Mn
1.5O
4(1-a) Li
2MnO
3(1-a) LiNi
0.5Mn
0.5O
2Material.
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| CN103715410A (en) * | 2012-09-29 | 2014-04-09 | 中信国安盟固利动力科技有限公司 | Anode material of high-energy composite lithium-ion battery |
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| CN111448690A (en) * | 2017-10-09 | 2020-07-24 | 科学与工业研究理事会 | Cathode material |
| CN114300673A (en) * | 2021-12-15 | 2022-04-08 | 惠州锂威新能源科技有限公司 | Lithium ion positive electrode composite material and preparation method thereof |
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| CN103715410A (en) * | 2012-09-29 | 2014-04-09 | 中信国安盟固利动力科技有限公司 | Anode material of high-energy composite lithium-ion battery |
| CN103311532A (en) * | 2013-05-24 | 2013-09-18 | 天津大学 | Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure |
| CN103311532B (en) * | 2013-05-24 | 2015-01-21 | 天津大学 | Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure |
| CN105229823A (en) * | 2013-07-30 | 2016-01-06 | 株式会社Lg化学 | Can additionally supply electrolytical secondary cell |
| CN105229822A (en) * | 2013-07-30 | 2016-01-06 | 株式会社Lg化学 | The lithium secondary battery that fail safe improves |
| US9812692B2 (en) | 2013-07-30 | 2017-11-07 | Lg Chem, Ltd. | Lithium secondary battery having enhanced safety |
| US10205137B2 (en) | 2013-07-30 | 2019-02-12 | Lg Chem, Ltd. | Secondary battery to which electrolyte can be additionally supplied |
| CN107406273A (en) * | 2015-03-06 | 2017-11-28 | 公立大学法人兵库县立大学 | Lithium nickel manganese composite oxide and its manufacture method and use its positive pole and electrical storage device |
| CN111448690A (en) * | 2017-10-09 | 2020-07-24 | 科学与工业研究理事会 | Cathode material |
| US11621416B2 (en) | 2017-10-09 | 2023-04-04 | Csir Campus | Cathode material |
| CN111448690B (en) * | 2017-10-09 | 2024-01-05 | 科学与工业研究理事会 | Cathode material |
| CN114300673A (en) * | 2021-12-15 | 2022-04-08 | 惠州锂威新能源科技有限公司 | Lithium ion positive electrode composite material and preparation method thereof |
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