CN100438195C - A Li-ion secondary battery - Google Patents
A Li-ion secondary battery Download PDFInfo
- Publication number
- CN100438195C CN100438195C CNB2004100273518A CN200410027351A CN100438195C CN 100438195 C CN100438195 C CN 100438195C CN B2004100273518 A CNB2004100273518 A CN B2004100273518A CN 200410027351 A CN200410027351 A CN 200410027351A CN 100438195 C CN100438195 C CN 100438195C
- Authority
- CN
- China
- Prior art keywords
- lithium
- stratiform
- spinel structure
- lithium manganate
- manganate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 106
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 69
- 239000011029 spinel Substances 0.000 claims abstract description 69
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 239000011149 active material Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000005536 Jahn Teller effect Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 21
- 230000008569 process Effects 0.000 description 18
- 239000011572 manganese Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 229910017052 cobalt Inorganic materials 0.000 description 13
- 239000010941 cobalt Substances 0.000 description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910015645 LiMn Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 2
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- 229910014282 N-NMP Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910015915 LiNi0.8Co0.2O2 Inorganic materials 0.000 description 1
- 229910012513 LiSbF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910006119 NiIn Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- TWFMKJHWXGLVDF-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O Chemical compound [Li].[Mn](=O)(=O)(O)O TWFMKJHWXGLVDF-UHFFFAOYSA-L 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000002411 thermogravimetry Methods 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
- 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
-
- 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
- H01M4/13—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
- H01M4/36—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
-
- 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)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention relates to a lithium ion secondary battery which comprises a positive pole, a negative pole, an electrolyte and a membrane, wherein an active material of the positive pole is formed by mixing spinel type lithium manganate and laminar nickel acid lithium according to a proportion of 1 to 9: 9 to 1 (part by weight), and the ratio of average particle diameters of the spinel type lithium manganate to the laminar nickel acid lithium is 1.5 to 8. The spinel type lithium manganate and the laminar nickel acid lithium are mixed and used by the present invention, the mixing ratio and the average particle diameters of the two kinds of substances are controlled, and thus, the orientating control of the spinel type lithium manganate to the laminar nickel acid lithium and the control of the laminar nickel acid lithium to the Jahn-Teller effect of the spinel type lithium manganate are realized. Therefore, a nonaqueous lighium secondary cell which has the advantages of low cost, high capacity, good heat stability, good high-current discharge performance and little attenuation under high temperatures is obtained.
Description
Technical field
The present invention relates to the battery that electric equipment products are used, particularly relate to a kind of lithium rechargeable battery.
Background technology
Along with developing rapidly of electronics industry, information industry, people are more and more higher to the requirement of all kinds of electric product power supplys, and wherein lithium rechargeable battery is widely used with its many superior function.The positive electrode that lithium battery uses mainly is an intercalation compounds, the at present operable stratiform cobalt acid lithium (LiCoO that mainly contains
2), stratiform lithium nickelate (LiNiO
2) and lithium manganate having spinel structure (LiMn
2O
4).The positive electrode of extensive use is stratiform cobalt acid lithium LiCoO
2Material.
Stratiform cobalt acid lithium and stratiform lithium nickelate and various derivative products (by the doping of zwitterion or the modes such as coating of other materials) thereof are though have higher specific discharge capacity, but their thermal stabilitys under charged state are relatively poor, and cobalt and nickel as raw material cost an arm and a leg, and have the problem of shortage of resources.
Though its raw material manganese resource content of lithium manganate having spinel structure is abundant, low price, and the thermal stability height under the charged state, thus the advantages such as security performance of battery improved, but it exists specific discharge capacity low, serious problems such as capacity attenuation is violent under the high temperature have limited its industrial applications.
For this reason, in Japanese patent laid-open 9-293538 and Chinese patent CN1262532A, propose to attempt improving the partial properties of lithium manganate having spinel structure by interpolation stratiform cobalt acid lithium and lithium nickelate in lithium manganate having spinel structure.But disclosed method and insufficient in the above-mentioned patent, mainly be when improving battery high-temperature shelf characteric and security performance, reduced the capacity of battery, perhaps improved technology difficulty that battery is made (requirement is done pole piece thin) or the like, and do not had fully to excavate the improvement effect of lithium manganate having spinel structure stratiform cobalt acid lithium and stratiform lithium nickelate.In addition, because stratiform lithium nickelate discharge platform (3.7V) is lower than stratiform cobalt acid lithium (3.8V), makes the stratiform lithium nickelate be better than stratiform cobalt acid lithium, so do not use stratiform cobalt acid lithium among the present invention the over effect of lithium manganate having spinel structure.
Also because the unit cell volume contraction when charging of lithium manganate having spinel structure material, and volumetric expansion when discharge, and overdischarge takes place in positive plate surface portion zone easily when discharge, the Jahn-Teller effect takes place, generate the relatively poor cubic system of chemical property, and this variation is at high temperature especially violent, becomes to cause the violent main cause of capacity attenuation under the lithium manganate having spinel structure high temperature.And on the other hand, stratiform cobalt acid lithium structure cell when charging expands, structure cell shrinks when discharge, and because cobalt acid lithium is a layer structure, the orientation height is easy to take place parallel-oriented with respect to collector body, thereby the impregnability based on electrolyte reduces, with than heavy-current discharge the time, transportable lithium ion quantity reduces, and causes the reduction of capacity.
Summary of the invention
The present invention is intended to effectively overcome lithium manganate having spinel structure and stratiform cobalt acid lithium and the stratiform lithium nickelate limitation separately as the positive source material, and provide a kind of excellent combination property, with low cost, the capacity height, Heat stability is good, good heavy current, the little lithium rechargeable battery of capacity attenuation under the high temperature.
For achieving the above object, the invention provides a kind of lithium rechargeable battery, this battery comprises positive pole, negative pole, electrolyte and barrier film, it is characterized in that, the active material of described positive pole is mixed by lithium manganate having spinel structure and stratiform lithium nickelate, its main purpose is, the two can produce on the change in volume complementary when discharging and recharging, thereby dissociating between the reduction active material particle, keep outside the higher current collecting efficiency, the stratiform lithium nickelate can effectively suppress overdischarge on the LiMn2O4 particle (because stratiform lithium nickelate electron conductivity is than lithium manganate having spinel structure height, therefore overdischarge at first occurs on the stratiform lithium nickelate particle), thus the generation of the Jahn-Teller effect of inhibition lithium manganate having spinel structure; Lithium manganate having spinel structure can play inhibitory action to the orientation trend of stratiform lithium nickelate.
In order to realize effect above-mentioned, with lithium manganate having spinel structure and the stratiform lithium nickelate mixed by 1~9: 9~1 (weight portions), its preferred mixed proportion is 3~7: 7~3.
In use, because the lithium manganate having spinel structure specific discharge capacity is lower, and tap density is slightly little, thereby causes lithium manganate having spinel structure system specific capacity very low.In order to satisfy the capacity requirement of battery, when using mixed cathode active material, must increase the anode dressing amount, thereby need higher anode dressing density, need bigger pressure to come compressing tablet during the positive plate film-making.If the lithium manganate having spinel structure average grain diameter is less than stratiform lithium nickelate average grain diameter, just can't the orientation trend of stratiform lithium nickelate under the high pressure be suppressed, the stratiform lithium nickelate takes place parallel-oriented with respect to collector body, the channel parallel of lithium ion migration is in collector body, and the electrolyte impregnability is not high, cause the difficulty of lithium ion migration, this problem is especially outstanding when heavy-current discharge.
If the average grain diameter of lithium manganate having spinel structure is greater than the average grain diameter of stratiform lithium nickelate.Lithium manganate having spinel structure can suppress the orientation of stratiform lithium nickelate, and promptly when applying big pressure, the pressure between lithium manganate having spinel structure and the stratiform lithium nickelate will suitably be disperseed.
It is 1.5~8 that the present invention requires the lithium manganate having spinel structure and the average grain diameter ratio of stratiform lithium nickelate, and its preferred average grain diameter ratio is 2~6.
Satisfying under the prerequisite of above-mentioned size ratio; if the average grain diameter of lithium manganate having spinel structure is too little; then the particle of stratiform lithium nickelate can be littler; in order to obtain the positive plate of satisfactory dressing density; need to use bigger pressure; thereby the orientation of stratiform lithium nickelate increases, and can cause the infiltration difficulty of electrolyte.If the average grain diameter of lithium manganate having spinel structure is excessive, the particle of stratiform lithium nickelate also needs corresponding increase, will cause the specific area of material to reduce, and reduces with the contact area of electrolyte, is unfavorable for battery performance.Therefore require that particle is generally between 5~40 μ m in the positive electrode of the present invention in the known particle size range of general positive electrode.
The structural formula of the lithium manganate having spinel structure of mentioning among the present invention is Li
1+xMn
2-yM
yO
4, wherein, M is at least a among element M g, Ca, Sr, Ba, Ti, Cr, Fe, Co, Ni, Cu, the Al, and the X value is-0.15~0.15, and the y value is 0~0.5.This shows that the structure of lithium manganate having spinel structure is not limited to LiMn
2O
4Structure, the material that the said structure formula is contained all can use, thereby improves the chemical property in a certain respect (for example specific discharge capacity, normal temperature, high temperature cyclic performance, storge quality, security performance or the like) of this positive electrode.
The structural formula of the stratiform lithium nickelate of mentioning among the present invention is LiNi
1-xM
xO
4, wherein, M is at least a among element M g, Ca, Sr, Ba, Ti, Cr, Mn, Fe, Co, Cu, the Al, the X value is 0~0.5.This shows that equally the structure of stratiform lithium nickelate is not limited to LiNiO
2Structure, the material that the said structure formula is contained all can use, thereby improves the chemical property in a certain respect (for example specific discharge capacity, normal temperature, high temperature cyclic performance, storge quality, security performance or the like) of this positive electrode.The preferred LiNi that uses among the present invention
0.8Co
0.2O
2Material.
The active material of positive pole of the present invention is to be mixed by lithium manganate having spinel structure and stratiform lithium nickelate, and add adhesive, conductive agent and solvent after mix, apply, oven dry, compressing tablet make.
Adhesive be fluorine resin and and polyethylene, polyvinyl alcohol; Conductive agent is carbon black, graphite-like material with carbon element; Solvent is N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol.
Contribution of the present invention is that it has effectively overcome lithium manganate having spinel structure and stratiform cobalt acid lithium and the stratiform lithium nickelate limitation separately as the positive source material.After the stratiform lithium nickelate mixing of contraction is used when expanding discharge when the lithium manganate having spinel structure of expansion is with charging when shrinking discharge during with charging, complementary except can when discharging and recharging, producing on the change in volume, thereby dissociating between the reduction active material particle, keep outside the higher current collecting efficiency, the stratiform lithium nickelate can effectively suppress overdischarge on the LiMn2O4 particle (because stratiform lithium nickelate electron conductivity is than lithium manganate having spinel structure height, therefore overdischarge at first occurs on the stratiform lithium nickelate particle), thus the generation of the Jahn-Teller effect of inhibition lithium manganate having spinel structure; Lithium manganate having spinel structure can play inhibitory action to the orientation trend of stratiform lithium nickelate.So just can obtain with low cost, capacity is high, the little non-water anode material of lithium battery of capacity attenuation under the Heat stability is good, good heavy current, high temperature.
Embodiment
The following example is to further explanation of the present invention and explanation, and the present invention is not constituted any limitation.
Lithium rechargeable battery of the present invention comprises positive pole, negative pole, electrolyte and barrier film, and wherein said negative pole is coated on the collector body by negative active core-shell material and corresponding adhesive, dispersant, solvent and oven dry, compressing tablet make.Described negative active core-shell material can use lithium metal, the lithium alloy material of doped lithium ion etc. that maybe can mix/go.As the material of the doped lithium ion that can mix/go, example is a carbonaceous material, as the product of roasting of native graphite, Delanium, coke, carbon black, RESEARCH OF PYROCARBON, carbon fiber and organic polymer; And chalcogenide, as the oxide and the sulfide of the doped lithium ion that mixes/go under can be in the lower current potential than positive pole.As carbonaceous material, mainly the carbonaceous material of being made up of graphite material (as native graphite and Delanium) is suitable.Described adhesive can be fluorine resins such as polytetrafluoroethylene, Kynoar and polyethylene, polyvinyl alcohol; Dispersant can be a cellulose; Solvent can be N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol, deionized water.As the collector body that is used for negative pole, can be Copper Foil, stainless steel foil, nickel foil, shape can be mesh-like, paper tinsel shape.Described electrolyte is non-aqueous electrolyte.To electrolyte wherein, the electrolytic salt that can use common nonaqueous electrolytic solution to use, for example LiPF
6, LiBF
4, LiAsF
6, LiClO
4, LiSbF
6, LiCl, LiBr, LiCF
2SO
3Deng lithium salts, consider from the oxidation stability angle, preferably select LiClO for use
4, LiPF
6, LiBF
4, LiAsF
6Solvent for use is an organic solvent, can be vinyl carbonate, propylene carbonate, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, 1,1-or 1,2-dimethoxy ethane, 1, one or more in 2-diethoxy ethane, oxolane, 2-methyltetrahydrofuran, methyl phenyl ethers anisole, ether, N-methyl pyrrolidone, dimethyl formamide, acetonitrile, propionitrile, chlorine nitrile, the ethyl acetate.Described barrier film can be nonwoven fabrics, synthetic resin microporous barrier, preferentially uses the synthetic resin microporous barrier, is excellent with polyolefin microporous film again wherein, and polyethene microporous membrane, microporous polypropylene membrane, polyethylene polypropylene composite micro porous film are specifically arranged.
Main points of the present invention are, the active material of described positive pole by lithium manganate having spinel structure and stratiform lithium nickelate by 1~9: the mixed of 9~1 (weight portions) forms, and the average grain diameter ratio of lithium manganate having spinel structure and stratiform lithium nickelate is 1.5~8.
Prepare lithium rechargeable battery of the present invention, described positive pole is that the lithium manganate having spinel structure that will prepare according to known method and stratiform lithium nickelate mix according to the above ratio and add adhesive, conductive agent and solvent, mixes, applies, oven dry, compressing tablet make.Wherein mixing speed is controlled to be 300~6000rpm, and mixing time is controlled to be 0.2~10 hour.Described adhesive can be fluorine resins such as polytetrafluoroethylene, Kynoar and polyethylene, polyvinyl alcohol; Conductive agent can be carbon black, graphite-like material with carbon element; Solvent can be N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol etc.
The following example can more help to illustrate the present invention.
Embodiment 1
At first preparing structural formula with known method is LiMn
2O
4Lithium manganate having spinel structure and the structural formula of the Co of doping be LiNi
0.8Co
0.2O
2The stratiform lithium nickelate, the stratiform lithium nickelate all refers to this kind material described in following examples and the Comparative Examples.The average grain diameter of control lithium manganate having spinel structure is 20 μ m, and stratiform lithium nickelate average grain diameter is 4 μ m, and the two particle diameter ratio is 5.
The lithium manganate having spinel structure of getting 8 parts (weight) mixes as positive electrode active materials mutually with the stratiform lithium nickelate of 1 part (weight).Adopting the polyvinylidene fluoride PVDF of 2% (weight) is adhesive, the acetylene black of 3% (weight) is conductive agent, the N-N-methyl-2-2-pyrrolidone N-NMP of surplus is a solvent, under the speed of 300~6000rpm, stirred 0.2~10 hour, make it to mix, apply then, oven dry, compressing tablet, wherein mix, apply, dry three processes and all need under vacuum environment, carry out, compressing tablet makes battery anode slice after being cut into specified size.
With the solvent N-N-methyl-2-2-pyrrolidone N-NMP of the adhesive polyvinylidene fluoride PVDF of the native graphite, 5% (weight) of 95% (weight) and surplus mix, apply, oven dry, compressing tablet, make battery cathode sheet after being cut into specified size.In addition, as the active material of negative plate, except using native graphite, can also use other material known, for example carbon black, coke, glass charcoal, charcoal fiber etc. or its mixture, perhaps lithium, lithium alloy etc.
Adopt above-mentioned positive plate, negative plate, electrolyte are lithium hexafluoro phosphate LiPF
6, solvent is the mixed organic solvents of vinyl carbonate, ethylene carbonate, diethyl carbonate, and concentration is 1 mol, and diaphragm paper is polyethylene, polypropylene composite diaphragm paper, promptly makes lithium rechargeable battery of the present invention by common process.
With the lithium rechargeable battery that above-mentioned positive pole and negative pole, electrolyte and barrier film are assembled into, have with low cost, capacity is high, advantages such as capacity attenuation is little under the Heat stability is good, good heavy current, high temperature.
Embodiment 2~embodiment 7 has provided the example of lithium manganate having spinel structure with the different mixed proportion of stratiform lithium nickelate, and its technical indicator test structure really sees Table 1.
Embodiment 2
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 7: 3 in this example, and other process is with embodiment 1.
Embodiment 3
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 5: 5 in this example, and other process is with embodiment 1.
Embodiment 4
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 3: 7 in this example, and other process is with embodiment 1.
Embodiment 5
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 1: 8 in this example, and other process is with embodiment 1.
Comparative Examples 1~4 has provided the experiment comparing result that positive electrode is respectively lithium manganate having spinel structure and stratiform lithium nickelate, and it the results are shown in Table 1.
Comparative Examples 1
Positive electrode uses lithium manganate having spinel structure in this example, and other process is with embodiment 1.
Comparative Examples 2
Positive electrode uses the stratiform lithium nickelate in this example, and other process is with embodiment 1.
Comparative Examples 3
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 15: 1 in this example, and other process is with embodiment 1.
Comparative Examples 4
The mixed proportion (weight portion) of lithium manganate having spinel structure and stratiform lithium nickelate is 1: 15 in this example, and other process is with embodiment 1.
The battery behavior test
Battery to embodiment and comparative example carries out performance test, and is as follows:
Specific discharge capacity: after the battery charge, be discharged to discharge capacity/positive electrode active materials quality of 3.0V with the electric current of 0.5C first from 4.2V, unit is mAh/g;
Circulation: be called once circulation at the current discharge with 1C to 3.0V with the 1C current charges then to 4.2V, the discharge capacity of acquisition is the capacity of this circulation, and unit is mAh;
High temperature circulation: under 60 ℃, be called once circulation at the current discharge with 1C to 3.0V with the 1C current charges then to 4.2V, the discharge capacity of acquisition is the capacity of this circulation, and unit is mAh;
100 circulation volume conservation rates: (the 100th circulation specific discharge capacity/specific discharge capacity first circulates) * 100%, unit is %;
100 high temperature circulation capability retentions (the 100th high temperature circulation specific discharge capacity/high temperature circulation specific discharge capacity) first * 100%, unit is %;
High-rate performance: with 1C, 3C electric current battery is discharged respectively, relatively the size of its discharge capacity is labeled as 3C/1C, and unit is %;
Thermal stability: the battery that will charge to 4.2V is dissected, and takes out positive plate, after the drying positive pole material is taken off, and carries out the thermogravimetric experiment under air atmosphere, obtains the decomposition temperature of this material, and unit is ℃.
Test result sees Table 1.
Table 1
Sequence number | Lithium manganate having spinel structure and stratiform lithium nickelate mixed proportion (weight portion) | Specific discharge capacity/mAh/g | 100 circulation volume conservation rate/% | 100 high temperature circulation capability retention/% | Heavy-current discharge performance (3C/1C)/% | Thermal stability/℃ |
Embodiment 1 | 8∶1 | 128 | 90 | 77 | 79 | 270 |
Embodiment 2 | 7∶3 | 135 | 91 | 82 | 78 | 252 |
Embodiment 3 | 5∶5 | 140 | 91 | 88 | 78 | 228 |
Embodiment 4 | 3∶7 | 149 | 91 | 87 | 77 | 215 |
Embodiment 5 | 1∶8 | 165 | 91 | 88 | 75 | 207 |
Comparative Examples 1 | 1 | 124 | 89 | 55 | 73 | 293 |
Comparative Examples 2 | 0 | 180 | 93 | 72 | 52 | 178 |
Comparative Examples 3 | 15∶1 | 125 | 89 | 56 | 73 | 281 |
Comparative Examples 4 | 1∶15 | 171 | 92 | 74 | 66 | 193 |
As can be seen from Table 1, lithium manganate having spinel structure and stratiform lithium nickelate are pressed lithium nickelate mass ratio X between 0.10~0.90 among the present invention, in the time of between being preferably 0.3~0.70, battery has superior comprehensive electrochemical properties, and its specific discharge capacity improves a lot with respect to spinelle manganic acid lithium material; (60 ℃) capacity attenuation is less under the high temperature; And good heavy current; Positive electrode active materials charging back decomposition temperature improves a lot with respect to lithium nickelate, and security performance is better.
Embodiment 8~15 has provided lithium manganate having spinel structure and stratiform lithium nickelate average grain diameter than (D
Mn/ D
Ni) experiment.
Embodiment 8
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 40 μ m mix (D
Mn/ D
Ni=0.5) use as positive active material, other process is with embodiment 1.
Embodiment 9
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 20 μ m mix (D
Mn/ D
Ni=1) use as positive active material, other process is with embodiment 1.
Embodiment 10
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 13 μ m mix (D
Mn/ D
Ni=1.54) use as positive active material, other process is with embodiment 1.
Embodiment 11
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 10 μ m mix (D
Mn/ D
Ni=2) use as positive active material, other process is with embodiment 1.
Embodiment 12
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 5 μ m mix (D
Mn/ D
Ni=4) use as positive active material, other process is with embodiment 1.
Embodiment 13
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 3.3 μ m mix (D
Mn/ D
Ni=6) use as positive active material, other process is with embodiment 1.
Embodiment 14
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 2.5 μ m mix (D
Mn/ D
Ni=8) use as positive active material, other process is with embodiment 1.
Embodiment 15
Be 3: 6 with mixed proportion in this example, average grain diameter is that the lithium manganate having spinel structure of 20 μ m and stratiform lithium nickelate that average grain diameter is 2 μ m mix (D
Mn/ D
Ni=10) use as positive active material, other process is with embodiment 1.
The battery behavior test, same first.
Test result sees Table 2.
Table 2
Sequence number | Average grain diameter compares D Mn/D Ni | Specific discharge capacity/mAh/g | 100 circulation volume conservation rate/% | 100 high temperature circulation capability retention/% | Heavy-current discharge performance (3C/1C)/% | Thermal stability/℃ |
Embodiment 8 | 0.5 | 135 | 87 | 78 | 56 | 231 |
Embodiment 9 | 1 | 142 | 90 | 82 | 62 | 231 |
Embodiment 10 | 1.5 | 141 | 91 | 85 | 73 | 230 |
Embodiment 11 | 2 | 140 | 92 | 88 | 79 | 230 |
Embodiment 12 | 4 | 141 | 91 | 88 | 79 | 229 |
Embodiment 13 | 6 | 139 | 91 | 84 | 75 | 229 |
Embodiment 14 | 8 | 140 | 92 | 85 | 70 | 226 |
Embodiment 15 | 10 | 136 | 89 | 84 | 63 | 220 |
By data in the table 2 as can be seen, lithium manganate having spinel structure is controlled at 1.5≤D with stratiform lithium nickelate average grain diameter ratio
Mn/ D
Ni≤ 8, preferably at 2≤D
Mn/ D
NiIn the time of between≤6, can guarantee the heavy-current discharge performance of positive electrode.
Claims (7)
1, a kind of lithium rechargeable battery, comprise positive pole, negative pole, electrolyte and barrier film, it is characterized in that, the active material of described positive pole by lithium manganate having spinel structure and stratiform lithium nickelate by 1~9: the mixed of 9~1 (weight portions) forms, and the average grain diameter ratio of lithium manganate having spinel structure and stratiform lithium nickelate is 1.5~8.
2, lithium rechargeable battery as claimed in claim 1 is characterized in that, the structural formula of described lithium manganate having spinel structure is Li
1+xMn
2-yM
yO
4, wherein, M is at least a among element M g, Ca, Sr, Ba, Ti, Cr, Fe, Co, Ni, Cu, the Al, and the X value is-0.15~0.15, and the y value is 0~0.5.
3, lithium rechargeable battery as claimed in claim 1 is characterized in that, the structural formula of layered lithium nickelate is LiNi
1-xM
xO
4, wherein, M is at least a among element M g, Ca, Sr, Ba, Ti, Cr, Mn, Fe, Co, Cu, the Al, the X value is 0~0.5.
4, lithium rechargeable battery as claimed in claim 1 is characterized in that, the mixed proportion of lithium manganate having spinel structure and stratiform lithium nickelate is 3~7: 7~3.
5, lithium rechargeable battery as claimed in claim 1 is characterized in that, lithium manganate having spinel structure is 2~6 with the average grain diameter ratio of stratiform lithium nickelate.
6, lithium rechargeable battery as claimed in claim 1, it is characterized in that, the active material of described positive pole is to be mixed by lithium manganate having spinel structure and stratiform lithium nickelate, and add adhesive, conductive agent and solvent after mix, apply, oven dry, compressing tablet make.
7, lithium rechargeable battery as claimed in claim 6 is characterized in that, described adhesive be fluorine resin and and polyethylene, polyvinyl alcohol; Conductive agent is carbon black, graphite-like material with carbon element; Solvent is N-methyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol.
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US9666862B2 (en) * | 2005-02-23 | 2017-05-30 | Lg Chem, Ltd. | Secondary battery of improved lithium ion mobility and cell capacity |
JP5118637B2 (en) | 2005-07-14 | 2013-01-16 | ボストン−パワー,インコーポレイテッド | Control electronics for Li-ion batteries |
JP5110556B2 (en) * | 2006-03-27 | 2012-12-26 | 日立マクセルエナジー株式会社 | Non-aqueous secondary battery and method of using the same |
TWI426678B (en) | 2006-06-28 | 2014-02-11 | Boston Power Inc | Electronics with multiple charge rate, battery packs, methods of charging a lithium ion charge storage power supply in an electronic device and portable computers |
CN101803070B (en) | 2007-06-22 | 2014-10-22 | 波士顿电力公司 | Cid retention device for li-ion cell |
JP2013504145A (en) | 2009-09-01 | 2013-02-04 | ボストン−パワー,インコーポレイテッド | Large scale storage battery system and assembly method |
WO2011099145A1 (en) * | 2010-02-12 | 2011-08-18 | トヨタ自動車株式会社 | Positive electrode active material for lithium secondary battery |
KR20140036148A (en) * | 2011-01-31 | 2014-03-25 | 미쓰비시 가가꾸 가부시키가이샤 | Non-aqueous electrolytic solution, and non-aqueous electrolyte secondary battery using same |
CN102315481A (en) * | 2011-08-29 | 2012-01-11 | 上海空间电源研究所 | High specific energy lithium-rich multi-element lithium ion battery and preparation method thereof |
CN103165897B (en) * | 2011-12-14 | 2016-04-27 | 比亚迪股份有限公司 | A kind of anode material for lithium-ion batteries, lithium ion cell positive and lithium ion battery |
CN102751482B (en) * | 2012-07-03 | 2014-12-03 | 四川大学 | High-performance lithium manganate anode material and preparation method thereof |
CN113675368B (en) * | 2021-09-01 | 2023-05-26 | 珠海冠宇电池股份有限公司 | Positive plate and lithium ion battery |
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