CN104733713A - Lithium-rich manganese material, application thereof and preparation method - Google Patents
Lithium-rich manganese material, application thereof and preparation method Download PDFInfo
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- CN104733713A CN104733713A CN201510133273.8A CN201510133273A CN104733713A CN 104733713 A CN104733713 A CN 104733713A CN 201510133273 A CN201510133273 A CN 201510133273A CN 104733713 A CN104733713 A CN 104733713A
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- lithium
- manganese
- sodium
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- rich lithium
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- 239000000463 material Substances 0.000 title claims abstract description 82
- 239000011572 manganese Substances 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000010405 anode material Substances 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 13
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 5
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 claims description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 33
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 229910052710 silicon Inorganic materials 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000013467 fragmentation Methods 0.000 claims description 13
- 238000006062 fragmentation reaction Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000008187 granular material Substances 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-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
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000007599 discharging Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 18
- 238000009413 insulation Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000004087 circulation Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 229910015177 Ni1/3Co1/3Mn1/3 Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910015118 LiMO Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910021314 NaFeO 2 Inorganic materials 0.000 description 2
- 229910016482 Ni0.4Co0.2Mn0.4 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 230000009466 transformation 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
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 ethyl carbonate ester Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium-rich manganese material, an application thereof and a preparation method. The lithium-rich manganese material is xLi<2-2b>Na2bMn<1-a>SiaO3.(1-x)Li<1-b>NabNi0.5Mn<0.5-a/2>Si<a/2>O2 and is used as an anode material. The preparation method comprises the following steps: (1) synthesizing a precursor material; (2) uniformly mixing the sodium salt and the lithium salt; and (3) sintering at high temperature. The prepared lithium-rich manganese material is nano-scale particle formed by stacking nano rod-shaped particles and is stable in structure, high in discharging specific capacity, high in primary efficiency, good in cycling stability and excellent in rate capability.
Description
Technical field
The present invention relates to field of lithium ion battery anode, be specifically related to a kind of rich lithium manganese material, its purposes and preparation method.
Background technology
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
2type solid-solution material, with performances such as its distinctive height ratio capacity (200 ~ 300mAh/g), outstanding circulation ability and new charge discharge mechanism, becomes the study hotspot of current lithium ion secondary battery anode material.
Commercial positive electrode (LiCoO
2, LiMn
2o
4, LiFePO
4) more and more can not meet the demand of people to high power capacity, high-energy-density electronic product, 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
2type solid-solution material, by the Li of stratiform
2mnO
3and LiMO
2(M=Mn, Ni, Co, Ni
0.5mn
0.5, Cr, Ni
1/3co
1/3mn
1/3, Fe ...) formed, with performances such as its distinctive height ratio capacity (200 ~ 300mAh/g), outstanding circulation ability and new charge discharge mechanism, become the study hotspot of current lithium ion secondary battery anode material.
Chinese patent (Zhao Yujuan, Sun Zhaoqin, Feng Hailan etc., a kind of synthetic method of spherical gradient lithium-rich anode material, China Patent No.: CN201010522413.8) discloses a kind of spherical gradient lithium-rich anode material xLi
2mnO
3(1-x) Li [Ni
0.4co
0.2mn
0.4] O
2the synthetic method of (0.1≤x≤0.4), with existing commercialization spherical precursor [Ni
0.4co
0.2mn
0.4] (OH)
2carry out Mn element coated, then with the process of the lithium hydroxide heat of mixing, 0.2C multiplying power current charge-discharge electricity, the specific capacitance that discharges first is 242mAh/g, and after 50 circulations, specific capacity is 221mAh/g.Chinese patent (Zhong Shengwen, Hu Wei, Zhang Qian, lithium-rich manganese-based anode material and preparation method thereof, China Patent No.: CN200910186311.0) discloses rich lithium base anode material Li [Li
(1-2x)/3ni
x-am
ymn
(2-x)/3-b] O
2(M=Co, Al, Ti, Mg, Cu) and preparation method thereof, adopts reactor Co deposited synthesis presoma [Ni
(x-a)/[x+ (2-x)/3]m
y/ [x+ (2-x)/3]mn
[(2-x)/3-b]/[x+ (2-x)/3]] (OH)
2, then with lithium compound mixing high temperature sintering, 0.1C multiplying power current charge-discharge electricity, putting specific capacitance is first 250mAh/g, and under the discharge and recharge condition of 2.75-4.2V, 1C, putting specific capacitance is first 144mAh/g, and after 300 circulations, capability retention is 97%.
These materials have excellent chemical property, but this kind of positive electrode exists following problem: 1. when initial charge is to more than 4.5V, irreversible electrochemical reaction occurs: xLi
2mn O
3(1-x) MO
2→ xMnO
2(1-x) MO
2+ xLi
2(there is reversible de-lithium reaction when charging is less than 4.5V: xLi in O
2mnO
3(1-x) LiMO
2→ xLi
2mnO
3(1-x) MO
2+ (1-x) Li.), the Li namely in material
+with Li
2the form of O is deviate from from structure cell, and during electric discharge, this part lithium ion all cannot be embedded into original structure cell again, and cause material to have larger irreversible capacity first, coulombic efficiency is lower.2. in cyclic process, there is phase transformation, voltage platform is decayed, and causes cyclical stability poor.3. the poor electric conductivity of material itself, in charge and discharge process, high rate performance is poor.
In order to address these problems, a lot of researcher carries out Surface coating process to it, mainly utilizes other metal or nonmetal oxide (such as, MgO, SiO
2, ZnO, Al
2o
3, ZrO
2deng) carry out Surface coating, improve coulombic efficiency first, improve cycle performance.Coating layer and rich lithium manganese material poor compatibility, interface impedance obviously increases; After coated, resistance increases more, and high rate performance declines many; And complicated process of preparation, therefore the more difficult application of rich lithium material of preparation at present.
In sum, in prior art, there is following technical problem: rich lithium manganese material has larger irreversible capacity first, and coulombic efficiency is lower, and cyclical stability is poor.
Summary of the invention
The object of the invention is to the shortcoming overcoming the existence of above-mentioned prior art, provide a kind of nouveaux riches' lithium manganese anode material and preparation method thereof, technique is simple, is easy to suitability for industrialized production.This rich lithium manganese material is xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2(0.1≤x≤0.9,0.005≤b≤0.08,0.005≤a≤0.15), has height ratio capacity, first coulombic efficiency high, and cycle performance is excellent, good rate capability.Prepare the persursor material of nickeliferous manganese silicon, mix with sodium salt, lithium salts, high temperature sintering obtains novel rich lithium manganese material, and technique is simple, is easy to suitability for industrialized production.Concrete technical scheme is as follows:
A kind of rich lithium manganese material is xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2.
Further, its micron particles piled up for nano bar-shape granule.
Further, 0.1≤x≤0.9,0.005≤b≤0.08,0.005≤a≤0.15.
The purposes of above-mentioned rich lithium manganese material, further, as positive electrode.
The preparation method of above-mentioned rich lithium manganese material, comprises the following steps:
(1) persursor material is synthesized;
(2) mix with sodium salt, lithium salts;
(3) high temperature sintering.
Further, step (1) comprises the steps:
(1-1) according to xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2in Ni, Mn, Si stoichiometric proportion take compound, the compound of manganese, the compound of silicon of nickel;
(1-2) mix;
(1-3) temperature programmed control sinters in air atmosphere;
(1-4) 650 ~ 750 DEG C are heated to 0.5 ~ 10 DEG C/min programming rate;
(1-5) 2 ~ 15h is incubated;
(1-6) room temperature is cooled to;
(1-7) broken, can persursor material be obtained.
Further, step (2) comprises the steps: according to xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2in Ni, Mn, Si, Na, Li stoichiometric proportion take persursor material, sodium salt, lithium salts, mix.
Further, Li excessive 1% ~ 5%, compensates when lithium salts at high temperature sinters and volatilizees on a small quantity.
Further, step (1) comprises the steps:
(3-1) temperature programmed control sinters in air atmosphere;
(3-2) 750 ~ 950 DEG C are heated to 0.5 ~ 10 DEG C/min programming rate;
(3-3) 3 ~ 48h is incubated;
(3-4) room temperature is cooled to;
(3-5) fragmentation is sieved, and can obtain rich lithium manganese anode material.
Further, the compound of described nickel is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride, nickel oxide, nickel hydroxide; And/or the compound of described manganese is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride, manganese oxide, manganous hydroxide; The compound of described silicon is one or more in tetraethoxysilane, silicon dioxide, the sub-silicon of oxidation; And/or described sodium salt is one or more in sodium carbonate, sodium acid carbonate, sodium chloride, sodium acetate, sodium nitrate, natrium nitrosum, sodium sulphate, sodium sulfite, sodium phosphate; And/or described lithium salts is one or more in lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride, lithium carbonate.
Compared with currently available technology, rich lithium manganese material prepared by the present invention is the micron particles that nano bar-shape granule is piled up, and Stability Analysis of Structures, has specific discharge capacity high, and efficiency is high first, good cycling stability, and high rate performance is excellent.Specifically: prepare presoma at 650 ~ 750 DEG C, material breakdown volume is reduced, when preparing rich lithium manganese material, be easy at high temperature storeroom and combine closely.Preparation xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2material, Si has stable chemical valence+4, and Si-O bond energy is far longer than Mn-O key bond energy, after Si replaces Mn, stabilizes the structure of material on the one hand, and reduces the generation of phase transformation; On the other hand, decrease the dissolving of Mn, make its stable cycle performance.Mixing of Na well reduces at initial charge to irreversible reaction [xLi during more than 4.5V
2mn O
3(1-x) MO
2→ xMnO
2(1-x) MO
2+ xLi
2o], thus improve efficiency first, ensure that simultaneously lithium deviate from after the stability of structure.The rich lithium manganese material prepared by this method is the micron particles that nano bar-shape granule is piled up, and conduct electricity very well, charge-discharge magnification performance is good.Its preparation technology is simple, is easy to suitability for industrialized production.
Accompanying drawing explanation
The rich lithium manganese material SEM of Fig. 1 prepared by the embodiment of the present invention 1 schemes.
The rich lithium manganese material first charge-discharge cycle performance curve of Fig. 2 prepared by the embodiment of the present invention 1.
The rich lithium manganese material charge-discharge performance curve of Fig. 3 prepared by the embodiment of the present invention 1.
Discharge under the rich lithium manganese material different multiplying of Fig. 4 prepared by the embodiment of the present invention 1 cycle performance curve.
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
A kind of rich lithium manganese anode material and preparation method thereof, comprises the following steps:
Step 1, synthesis persursor material
According to xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2in Ni, Mn, Si stoichiometric proportion take compound, the compound of manganese, the compound of silicon of nickel, mix, then temperature programmed control sinters in air atmosphere, 650 ~ 750 DEG C are heated to 0.5 ~ 10 DEG C/min programming rate, insulation 2 ~ 15h, be cooled to room temperature, broken, can persursor material be obtained.
Step 2, prepare rich lithium manganese material
According to xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2in Ni, Mn, Si, Na, Li stoichiometric proportion take persursor material, sodium salt, lithium salts (Li excessive 1% ~ 5%, Li is slightly excessive is volatilize on a small quantity to compensate when lithium salts at high temperature sinters), mix, then temperature programmed control sinters in air atmosphere, be heated to 750 ~ 950 DEG C with 0.5 ~ 10 DEG C/min programming rate, insulation 3 ~ 48h, is cooled to room temperature, fragmentation is sieved, and can obtain rich lithium manganese anode material.
Particle diameter when the cumulative particle sizes percentile of described rich lithium manganese anode material reaches 50% corresponding to (D50) is 5 ~ 16 μm, and specific area is 0.3 ~ 1.2m
2/ g, tap density is 1.9 ~ 2.5g/cm
3.。The compound of described nickel is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride, nickel oxide, nickel hydroxide.The compound of described manganese is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride, manganese oxide, manganous hydroxide.The compound of described silicon is one or more in tetraethoxysilane, silicon dioxide, the sub-silicon of oxidation.Described sodium salt is one or more in sodium carbonate, sodium acid carbonate, sodium chloride, sodium acetate, sodium nitrate, natrium nitrosum, sodium sulphate, sodium sulfite, sodium phosphate.Described lithium salts is one or more in lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride, lithium carbonate.
Embodiment 1
The present embodiment provides a kind of rich lithium manganese anode material and preparation method thereof, and this rich lithium manganese material is 0.5Li
1.98na
0.02mn
0.98si
0.02o
30.5Li
0.99na
0.01ni
0.5mn
0.49si
0.01o
2, it comprises the following steps:
Step 1, synthesis persursor material
According to 0.5Li
1.98na
0.02mn
0.98si
0.02o
30.5Li
0.99na
0.01ni
0.5mn
0.49si
0.01o
2in Ni, Mn, Si stoichiometric proportion take nickel oxide, manganese acetate, silicon dioxide, mix, then temperature programmed control sinters in air atmosphere, be heated to 650 DEG C with 3 DEG C/min programming rate, insulation 5h, is cooled to room temperature, fragmentation, can obtain persursor material.
Step 2, prepare rich lithium manganese material
According to 0.5Li
1.98na
0.02mn
0.98si
0.02o
30.5Li
0.99na
0.01ni
0.5mn
0.49si
0.01o
2in Ni, Mn, Si, Na, Li stoichiometric proportion take persursor material, sodium carbonate, lithium carbonate (Li excessive 2%, Li is slightly excessive is volatilize on a small quantity to compensate when lithium salts at high temperature sinters), mix, then temperature programmed control sinters in air atmosphere, be heated to 850 DEG C with 4 DEG C/min programming rate, insulation 20h, is cooled to room temperature, fragmentation is sieved, and can obtain rich lithium manganese anode material.
As shown in Figure 1, SEM test result shows, the rich lithium manganese material of preparation is the micron particles that nano bar-shape granule is piled up, and particle diameter D50 is 9.6 μm after tested, and specific area is 0.85m
2/ g, tap density is 2.1g/cm
3.
The preparation method of battery pole piece:
Positive electrode is mixed according to mass ratio 8:1:1 with conductive agent acetylene black, binding agent PVDF (Kynoar), with NMP (1-Methyl-2-Pyrrolidone), this mixture is modulated into slurry, evenly be coated on aluminium foil, put into baking oven, dry 3h for 110 DEG C, take out and be washed into pole piece, 85 DEG C of vacuumize 12 hours, carry out compressing tablet, 85 DEG C of vacuumize 12 hours, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is 1.0mol/L LiPF
6eC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1:1) solution, barrier film is celgard2325 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
As shown in Figure 2, first charge-discharge loop test is carried out to this button cell: charging/discharging voltage scope is 4.8 ~ 2.0V, be the condition of 0.1C (1C=220mA/g) at charging and discharging currents under, first charge-discharge specific capacity is respectively 264.42mAh/g, 232.904mAh/g, initial coulomb efficiency is 88.08%, and coulombic efficiency is higher first.
Cycle performance is tested: the 1-3 time cycle charge-discharge electric current is 0.1C, and the 4-94 time cycle charge-discharge electric current is 0.2C (1C=220mA/g).Be the condition of 0.2C at charging and discharging currents under, first discharge specific capacity is 228.102mAh/g, and 90 specific capacities that circulate are 220.803mAh/g, and capability retention is 96.8%, and cycle performance is better.As shown in Figure 3, can find out that in charge and discharge cycles process, voltage platform does not almost decline (mean voltage reduces by 1.1%), charging and discharging curve is reproducible, i.e. good cycling stability.
As shown in Figure 4, high rate performance test is carried out to this button cell: charging/discharging voltage scope is 4.8 ~ 2.0V, and charging current is 0.1C, and discharging current is respectively 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, each circulation 5 times, wherein, 1C=220mA/g.High rate performance test result shows, 5C specific discharge capacity is at more than 150mAh/g, and high rate performance is better, and good rate capability comes from its composition, structure.
Embodiment 2
The present embodiment provides a kind of rich lithium manganese anode material and preparation method thereof, and this rich lithium manganese material is 0.55Li
1.90na
0.10mn
0.98si
0.02o
30.45Li
0.95na
0.05ni
0.5mn
0.49si
0.01o
2, it comprises the following steps:
Step 1, synthesis persursor material
According to 0.55Li
1.90na
0.10mn
0.98si
0.02o
30.45Li
0.95na
0.05ni
0.5mn
0.49si
0.01o
2in Ni, Mn, Si stoichiometric proportion take nickel nitrate, manganese nitrate, silicon dioxide, mix, then temperature programmed control sinters in air atmosphere, be heated to 700 DEG C with 3 DEG C/min programming rate, insulation 4h, is cooled to room temperature, fragmentation, can obtain persursor material.
Step 2, prepare rich lithium manganese material
According to 0.55Li
1.90na
0.10mn
0.98si
0.02o
30.45Li
0.95na
0.05ni
0.5mn
0.49si
0.01o
2in Ni, Mn, Si, Na, Li stoichiometric proportion take persursor material, sodium carbonate, lithium acetate (Li excessive 1%, Li is slightly excessive is volatilize on a small quantity to compensate when lithium salts at high temperature sinters), mix, then temperature programmed control sinters in air atmosphere, be heated to 750 DEG C with 5 DEG C/min programming rate, insulation 10h, is cooled to room temperature, fragmentation is sieved, and can obtain rich lithium manganese anode material.
The rich lithium manganese material prepared after tested particle diameter D50 is 5.8 μm, and specific area is 1.2m
2/ g, tap density is 1.95g/cm
3.
Assembled battery and method of testing are all with embodiment 1, and test data is in table 1.
Embodiment 3
The present embodiment provides a kind of rich lithium manganese anode material and preparation method thereof, and this rich lithium manganese material is 0.3Li
1.98na
0.02mn
0.90si
0.10o
30.7Li
0.99na
0.01ni
0.5mn
0.45si
0.05o
2, it comprises the following steps:
Step 1, synthesis persursor material
According to 0.3Li
1.98na
0.02mn
0.90si
0.10o
30.7Li
0.99na
0.01ni
0.5mn
0.45si
0.05o
2in Ni, Mn, Si stoichiometric proportion take nickel chloride, manganese sulfate, tetraethoxysilane, mix, then temperature programmed control sinters in air atmosphere, be heated to 660 DEG C with 5 DEG C/min programming rate, insulation 10h, is cooled to room temperature, fragmentation, can obtain persursor material.
Step 2, prepare rich lithium manganese material
According to 0.3Li
1.98na
0.02mn
0.90si
0.10o
30.7Li
0.99na
0.01ni
0.5mn
0.45si
0.05o
2in Ni, Mn, Si, Na, Li stoichiometric proportion take persursor material, sodium phosphate, lithium hydroxide (Li excessive 5%, Li is slightly excessive is volatilize on a small quantity to compensate when lithium salts at high temperature sinters), mix, then temperature programmed control sinters in air atmosphere, be heated to 950 DEG C with 8 DEG C/min programming rate, insulation 15h, is cooled to room temperature, fragmentation is sieved, and can obtain rich lithium manganese anode material.
The rich lithium manganese material prepared after tested particle diameter D50 is 15 μm, and specific area is 0.42m
2/ g, tap density is 2.35g/cm
3.
Assembled battery and method of testing are all with embodiment 1, and test data is in table 1.
Embodiment 4
The present embodiment provides a kind of rich lithium manganese anode material and preparation method thereof, and this rich lithium manganese material is 0.6Li
1.84na
0.16mn
0.98si
0.02o
30.4Li
0.92na
0.08ni
0.5mn
0.49si
0.01o
2, it comprises the following steps:
Step 1, synthesis persursor material
According to 0.6Li
1.84na
0.16mn
0.98si
0.02o
30.4Li
0.92na
0.08ni
0.5mn
0.49si
0.01o
2in Ni, Mn, Si stoichiometric proportion take nickel oxide, manganese acetate, tetraethoxysilane, mix, then temperature programmed control sinters in air atmosphere, be heated to 680 DEG C with 5 DEG C/min programming rate, insulation 6h, is cooled to room temperature, fragmentation, can obtain persursor material.
Step 2, prepare rich lithium manganese material
According to 0.6Li
1.84na
0.16mn
0.98si
0.02o
30.4Li
0.92na
0.08ni
0.5mn
0.49si
0.01o
2in Ni, Mn, Si, Na, Li stoichiometric proportion take persursor material, sodium acid carbonate, lithium nitrate (Li excessive 2%, Li is slightly excessive is volatilize on a small quantity to compensate when lithium salts at high temperature sinters), mix, then temperature programmed control sinters in air atmosphere, be heated to 800 DEG C with 4 DEG C/min programming rate, insulation 17h, is cooled to room temperature, fragmentation is sieved, and can obtain rich lithium manganese anode material.
The rich lithium manganese material prepared after tested particle diameter D50 is 8.5 μm, and specific area is 0.81m
2/ g, tap density is 1.99g/cm
3.
Assembled battery and method of testing are all with embodiment 1, and test data is in table 1.
Embodiment 5
The present embodiment provides a kind of rich lithium manganese anode material and preparation method thereof, and this rich lithium manganese material is 0.65Li
1.98na
0.02mn
0.86si
0.14o
30.35Li
0.99na
0.01ni
0.5mn
0.43si
0.07o
2, it comprises the following steps:
Step 1, synthesis persursor material
According to 0.65Li
1.98na
0.02mn
0.86si
0.14o
30.35Li
0.99na
0.01ni
0.5mn
0.43si
0.07ni, Mn, Si stoichiometric proportion in O takes nickel oxide, manganese acetate, silicon dioxide, and mix, then temperature programmed control sinters in air atmosphere, be heated to 690 DEG C with 3 DEG C/min programming rate, insulation 4h, is cooled to room temperature, fragmentation, can obtain persursor material.
Step 2, prepare rich lithium manganese material
According to 0.65Li
1.98na
0.02mn
0.86si
0.14o
30.35Li
0.99na
0.01ni
0.5mn
0.43si
0.07ni, Mn, Si, Na, Li stoichiometric proportion in O takes persursor material, sodium carbonate, lithium carbonate (Li excessive 3%, Li is slightly excessive is volatilize on a small quantity to compensate when lithium salts at high temperature sinters), mix, then temperature programmed control sinters in air atmosphere, be heated to 850 DEG C with 4 DEG C/min programming rate, insulation 15h, is cooled to room temperature, fragmentation is sieved, and can obtain rich lithium manganese anode material.
The rich lithium manganese material prepared after tested particle diameter D50 is 7.2 μm, and specific area is 1.01m
2/ g, tap density is 1.94g/cm
3.
Assembled battery and method of testing are all with embodiment 1, and test data is in table 1.
The rich lithium manganese anode material discharge cycles test data of table 1 prepared by the embodiment of the present invention.
Remarks:
η=(U1-U2)/U1, U1 is that 0.2C circulation is discharged mean voltage first, and U2 is that 0.2C circulates the 90th electric discharge mean voltage.
Above by reference to the accompanying drawings to invention has been exemplary description; obvious specific implementation of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that method of the present invention is conceived and technical scheme is carried out; or directly apply to other occasion, all within protection scope of the present invention without improving.
Claims (10)
1. a rich lithium manganese material, is characterized in that, is xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2.
2. rich lithium manganese material as claimed in claim 1, is characterized in that, its micron particles piled up for nano bar-shape granule.
3. rich lithium manganese material as claimed in claim 1 or 2, is characterized in that, 0.1≤x≤0.9,0.005≤b≤0.08,0.005≤a≤0.15.
4. the purposes of rich lithium manganese material as described in claim 1-3, is characterized in that, as positive electrode.
5. the preparation method of rich lithium manganese material as described in claim 1-3, is characterized in that, comprise the following steps:
(1) persursor material is synthesized;
(2) mix with sodium salt, lithium salts;
(3) high temperature sintering.
6. the preparation method of rich lithium manganese material as claimed in claim 5, it is characterized in that, step (1) comprises the steps:
(1-1) according to xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2in Ni, Mn, Si stoichiometric proportion take compound, the compound of manganese, the compound of silicon of nickel;
(1-2) mix;
(1-3) temperature programmed control sinters in air atmosphere;
(1-4) 650 ~ 750 DEG C are heated to 0.5 ~ 10 DEG C/min programming rate;
(1-5) 2 ~ 15h is incubated;
(1-6) room temperature is cooled to;
(1-7) broken, can persursor material be obtained.
7. the preparation method of rich lithium manganese material as described in claim 5 or 6, it is characterized in that, step (2) comprises the steps: according to xLi
2-2bna
2bmn
1-asi
ao
3(1-x) Li
1-bna
bni
0.5mn
0.5-a/2si
a/2o
2in Ni, Mn, Si, Na, Li stoichiometric proportion take persursor material, sodium salt, lithium salts, mix.
8. the preparation method of rich lithium manganese material as claimed in claim 7, is characterized in that, Li excessive 1% ~ 5%, compensates when lithium salts at high temperature sinters and volatilizees on a small quantity.
9. the preparation method of rich lithium manganese material according to any one of claim 5-8, it is characterized in that, step (1) comprises the steps:
(3-1) temperature programmed control sinters in air atmosphere;
(3-2) 750 ~ 950 DEG C are heated to 0.5 ~ 10 DEG C/min programming rate;
(3-3) 3 ~ 48h is incubated;
(3-4) room temperature is cooled to;
(3-5) fragmentation is sieved, and can obtain rich lithium manganese anode material.
10. the preparation method of rich lithium manganese material according to any one of claim 5-9, is characterized in that, the compound of described nickel is one or more in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride, nickel oxide, nickel hydroxide; And/or the compound of described manganese is one or more in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride, manganese oxide, manganous hydroxide; The compound of described silicon is one or more in tetraethoxysilane, silicon dioxide, the sub-silicon of oxidation; And/or described sodium salt is one or more in sodium carbonate, sodium acid carbonate, sodium chloride, sodium acetate, sodium nitrate, natrium nitrosum, sodium sulphate, sodium sulfite, sodium phosphate; And/or described lithium salts is one or more in lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride, lithium carbonate.
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| CN115000399A (en) * | 2022-05-25 | 2022-09-02 | 西安交通大学 | Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522537A (en) * | 2011-11-25 | 2012-06-27 | 李溪 | Simple method for preparing manganese-based laminated anode material with high electrochemical performances by metal-doping |
| CN103199235A (en) * | 2013-03-28 | 2013-07-10 | 浙江大学 | Tubular composite material as well as preparation method and application thereof |
| CN103490051A (en) * | 2013-09-18 | 2014-01-01 | 成都晶元新材料技术有限公司 | Multi-element anode lithium battery material suitable for high voltage and preparation method for material |
| CN103915617A (en) * | 2014-04-18 | 2014-07-09 | 东莞市迈科科技有限公司 | Lithium-rich positive material and preparation method thereof |
-
2015
- 2015-03-25 CN CN201510133273.8A patent/CN104733713A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102522537A (en) * | 2011-11-25 | 2012-06-27 | 李溪 | Simple method for preparing manganese-based laminated anode material with high electrochemical performances by metal-doping |
| CN103199235A (en) * | 2013-03-28 | 2013-07-10 | 浙江大学 | Tubular composite material as well as preparation method and application thereof |
| CN103490051A (en) * | 2013-09-18 | 2014-01-01 | 成都晶元新材料技术有限公司 | Multi-element anode lithium battery material suitable for high voltage and preparation method for material |
| CN103915617A (en) * | 2014-04-18 | 2014-07-09 | 东莞市迈科科技有限公司 | Lithium-rich positive material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115000399A (en) * | 2022-05-25 | 2022-09-02 | 西安交通大学 | Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
| CN115000399B (en) * | 2022-05-25 | 2023-07-25 | 江苏聚烽新能源科技有限公司 | Spherical-like sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
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Application publication date: 20150624 |