CN102208602B - Lithium manganese silicate/nanometer oxide composite anode material and preparation method thereof - Google Patents
Lithium manganese silicate/nanometer oxide composite anode material and preparation method thereof Download PDFInfo
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- CN102208602B CN102208602B CN2011101097250A CN201110109725A CN102208602B CN 102208602 B CN102208602 B CN 102208602B CN 2011101097250 A CN2011101097250 A CN 2011101097250A CN 201110109725 A CN201110109725 A CN 201110109725A CN 102208602 B CN102208602 B CN 102208602B
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000010405 anode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 38
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000011572 manganese Substances 0.000 claims abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- ASTZLJPZXLHCSM-UHFFFAOYSA-N dioxido(oxo)silane;manganese(2+) Chemical compound [Mn+2].[O-][Si]([O-])=O ASTZLJPZXLHCSM-UHFFFAOYSA-N 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000001354 calcination Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 26
- 238000009413 insulation Methods 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 229940071125 manganese acetate Drugs 0.000 claims description 7
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 5
- 235000006748 manganese carbonate Nutrition 0.000 claims description 5
- 239000011656 manganese carbonate Substances 0.000 claims description 5
- 229940093474 manganese carbonate Drugs 0.000 claims description 5
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 5
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 5
- 239000002071 nanotube Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- WNKMTAQXMLAYHX-UHFFFAOYSA-N barium(2+);dioxido(oxo)titanium Chemical compound [Ba+2].[O-][Ti]([O-])=O WNKMTAQXMLAYHX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004567 concrete Substances 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 3
- 239000010419 fine particle Substances 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 230000004087 circulation Effects 0.000 description 14
- 239000011858 nanopowder Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 238000013019 agitation Methods 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000012216 screening Methods 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- -1 Polypropylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a lithium manganese silicate/nanometer oxide composite anode material and a preparation method thereof, belonging to the technical field of electrochemical power supply material preparation. The anode material comprises 98-99.9 wt% of lithium manganese silicate and 0.1-2 wt% of nanometer oxide. The preparation method comprises the steps of: modifying the electrical property of the lithium manganese silicate by using the nanometer oxide; preparing the composite material by using a sol-gel method; mixing and dissolving a raw material at a lithium position, a raw material at a manganese position, a raw material at a silicon position, a complexing agent and the nanometer oxide; and ultrasonically treating in a vacuum state, drying and refining, and preparing lithium manganese silicate/nanometer powder tube oxide composite powders with fine particles, good crystalline properties and uniform components through controlling the temperature and time of heat treatment. Compared with a single-phase lithium manganese silicate, the lithium manganese silicate can be obviously improved in electrochemical property. As an anode material, the lithium manganese silicate/nanometer oxide composite material disclosed by the invention has extensive application prospect in the field of lithium ion batteries.
Description
Technical field
The invention belongs to the electrochemical power source technical field of material, relate in particular to a kind of lithium ion battery lithium manganese silicate/nanometer oxide composite anode material and preparation method thereof.
Technical background
At first proposed Li in US Patent No. 6085015 by people such as Armand in 2000
2MnSiO
4Possibility as anode material for lithium-ion batteries.(Electrochemistry Communications, 2004,6 (11): 1144-1148) calculated theoretically Li such as Zhou Fei in 2004
2MnSiO
4Embedding lithium current potential and the change in volume of material.2006, R.Dominko and research group thereof adopted and improve sol-gel process, utilize citric acid to synthesize first Li as complexing agent
2MnSiO
4Positive electrode.Li
2MnSiO
4Have that theoretical capacity height, cyclical voltage can be accepted, fail safe is good, the advantage such as environmental friendliness, cost of material are cheap, be considered to up-and-coming anode material for lithium-ion batteries candidate material.
Li
2MnSiO
4Theoretical capacity is up to 333mAh/g, but at present actual capacity also relatively low, Capacity fading is serious.The Li that R.Dominko etc. are synthetic
2MnSiO
4Material first circulating and reversible capacity only is about 100 mAh/g.The people such as Yang (Journal of Power Sources, 2007,174 (2): 528-532) synthetic Li
2MnSiO
4Material when current density is that the first discharge capacity of 5mA/g is 209 mAh/g, decays to 140 mAh/g through discharge capacity after 10 circulations; When current density was 150mA/g, discharge capacity only was 135 mAh/g first.For Li
2MnSiO
4Actual capacity is the serious problem of relatively low, Capacity fading also, and the modified measures of report mainly contains following several at present: (1) carbon dope is composite modified, adopts wet chemistry method to introduce sucrose in raw material such as people such as Yang, synthesis nano Li
2MnSiO
4/ C combination electrode material; (2) impurity modification, for example, Chinese patent Granted publication CN 100438155C, Chen Zhao bravely waits people's (silicate journal, 2010,38 (3), 409-413) and people (the Electrochemical Solid-State Letters such as Yang, 2006,9 (12): A542-A544) synthetic manganese position Li doped
2Mn
0.5Fe
0.5SiO
4Positive electrode, the people such as Xu Wengang (silicate circular, 2009,28 (3), 464-467) synthetic Li
2Mn
0.95Mg
0.05SiO
4Positive electrode.At present for Li
2MnSiO
4The research of material is abundant not enough, and its circulation volume, cyclical stability etc. all also have very large room for promotion.
Summary of the invention
The purpose of this invention is to provide a kind of lithium manganese silicate/nanometer oxide composite anode material and preparation method thereof.
A kind of lithium manganese silicate/nanometer oxide composite anode material is characterized in that, this composite positive pole comprises 98-99.9 wt % manganese silicate of lithium (Li
2MnSiO
4) and the nano-oxide of 0.1-2wt%.
A kind of preparation method of lithium manganese silicate/nanometer oxide composite anode material is characterized in that, the method utilizes nano-oxide to modify the manganese silicate of lithium electrical property, and concrete steps are as follows:
Being lithium raw material, manganese raw material and silicon raw material with parent stock mixes by Li ﹕ Mn ﹕ Si=2 ﹕ 1 ﹕ 1,0.1～1.5 times the enveloping agent solution that adds the manganese silicate of lithium mole, stirring and dissolving is homogeneous solution, then the nano-oxide that adds manganese silicate of lithium quality 1～5%, stir and ultrasonic processing 0.2～1h, vacuum is taken out 60～120 ℃ of heat treated and stirring after removing bubble processing 1～6h, obtains gel; Refinement after dry, with powder calcination processing in inert atmosphere, calcine technology is step multistage heat treatment, the low-temperature zone heating rate is 1～3 ℃/min, rises to 350～550 ℃, insulation 2～8h; Continue, heating rate is 2～8 ℃/min, rises to 650～850 ℃, and insulation 6～20h obtains lithium manganese silicate/nanometer oxide composite anode material.
Described lithium raw material is a kind of in lithium acetate, Lithium hydroxide monohydrate, lithium carbonate, lithium chloride, the lithium nitrate, or its mixture; Described manganese raw material is a kind of of manganese acetate, manganese chloride, manganese carbonate, manganese sulfate, or its mixture; Described silicon raw material is a kind of in tetraethoxysilane, the silicon dioxide, or its mixture.
Described nano-oxide is the nano level oxide of powdery, perhaps is the oxide of tubular nanometer level, perhaps is the oxide of the hybrid nanoscale of powdery and tubulose.
Described nano-oxide is selected from: nano alumina powder, nanometer titanium dioxide titanium valve, nano oxidized zirconium powder, nano zinc oxide powder, nano barium titanate powder, nano titanium dioxide pipe or nanotubes of titanic acid, or two or more mixture in them.
Described complexing agent is selected from citric acid, tartaric acid, or its mixture, or their mixtures after by dissolution with solvents.
Described solvent is a kind of in deionized water, ethanol, isopropyl alcohol and the acetone, or its mixture.
Described ultrasonic processing has activated the surface of nano-oxide, manganese silicate of lithium be connected the composite material of oxide and connected by the interface of chemical bonding; Perhaps, the nano-oxide after the ultrasonic processing activation is distributed in the manganese silicate of lithium particle surface or is embedded in the gap of manganese silicate of lithium particle.
Beneficial effect of the present invention utilizes nano-oxide to modify the manganese silicate of lithium electrical property, adopt sol-gel process to prepare composite material, with the lithium raw material, manganese raw material, silicon raw material, complexing agent and nano-oxide mixed dissolution, ultrasonic vacuum treatment is after the dry refinement, by control heat treatment temperature and time, it is tiny to prepare particle, and crystal property is good, the lithium manganese silicate/nanometer oxide composite granule of homogeneous chemical composition.Described lithium manganese silicate/nanometer oxide composite anode material is applied to secondary lithium battery, compares with single-phase manganese silicate of lithium, can significantly improve the chemical property of manganese silicate of lithium.Lithium manganese silicate/nanometer oxide composite material provided by the invention is with a wide range of applications in the lithium ion battery field as positive electrode.
Description of drawings
Fig. 1 is the XRD diffraction spectra of embodiment 1 mesosilicic acid manganese lithium/titanic oxide nano composite positive pole.
Fig. 2 is the SEM shape appearance figure of embodiment 1 mesosilicic acid manganese lithium/titanic oxide nano composite positive pole.Manganese silicate of lithium/titanic oxide nano composite positive pole granular size is comparatively even as can be seen from Fig. 2, and major part is 1-2 μ m.
Fig. 3 is the discharge capacity figure of embodiment 1 mesosilicic acid manganese lithium/titanic oxide nano composite positive pole.
Embodiment
The invention provides a kind of lithium manganese silicate/nanometer oxide composite anode material and preparation method thereof.Below by embodiment, outstanding feature of the present invention and distinguishing feature are further elaborated, only be the present invention is described and never limit the present invention.
Weighing lithium acetate LiAc2H
2O 10.202 g, manganese acetate Mn (Ac)
24H
2O 12.7799 g and tetraethoxysilane (C
8H
20O
4Si) 10.4165 g join 120 ml and are dissolved with 9.606 g citric acid (C
6H
8O
7) absolute ethyl alcohol in mix to settled solution; Then add 0.0081 g titanium dioxide TiO
2Nano powder; Ultrasonic 0.2 h after vacuum removal bubble is processed 1 h, takes out 60 ℃ of heat treated and stirs, and obtains gel after solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 1 ℃/min, rises to 350 ℃ of calcining 2h with powder; Continuation rises to 650 ℃ of calcining insulation 6h with the heating rate of 2 ℃/min, obtains manganese silicate of lithium/titanic oxide nano composite positive pole.
The chemical property of gained positive electrode is measured as follows: take by weighing 0.435 g positive powder and 0.025 g acetylene black places the 1-METHYLPYRROLIDONE that is dissolved with 0.04 g Kynoar, supersonic oscillations are mixed 30min, magnetic agitation 24h fully mixes in the flat measuring cup, the furnishing uniform sizing material; Be coated on the collector aluminium foil, 80 ℃ of dryings, but flatten at the warm-up mill press, make the anode thin film of the about 200 μ m of thickness; The pole piece film of handling well is washed into the disk of Φ 9 mm; It more than 120 ℃ of vacuumize 12 h, is naturally taken out after the cooling and weigh, as backup electrode; Electrolyte adopts 1 mol/L LiPF
6Ethyl carbonate EC: dimethyl carbonate DMC (1:1) mixed liquor; Polypropylene microporous film is barrier film; Metal lithium sheet is as negative pole; Packaged battery in the glove box of argon gas atmosphere, ageing 24 h; Press the constant current charge-discharge system, the speed of 0.05C charges to 4.8 V, and the speed of 0.05C is discharged to 1.5 V, and first discharge specific capacity is about 214.5 mAh/g, and specific discharge capacity is 133.1 mAh/g after 10 circulations.
Embodiment 2
Weighing lithium acetate LiAc2H
2O 10.202 g, manganese acetate Mn (Ac)
24H
2O 12.7799 g and tetraethoxysilane (C
8H
20O
4Si) 10.4165 g join 150 ml and are dissolved with 11.5272 g citric acid (C
6H
8O
7) alcohol in mix to settled solution; Then add 1.2 g titanium dioxide TiO
2Nano powder; Ultrasonic 0.3 h after vacuum removal bubble is processed 1.5 h, takes out 70 ℃ and adds thermal agitation, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 1 ℃/min, rises to 450 ℃ of calcining 4h with powder; Continuation rises to 750 ℃ of calcining insulation 7h with the heating rate of 4 ℃/min, obtains manganese silicate of lithium/titanic oxide nano composite positive pole.
Weighing lithium hydroxide LiOHH
2O 4.195 g, manganese acetate Mn (Ac)
24H
2O 12.7799 g and silicon dioxide SiO
23.0045 g joins 145 ml and is dissolved with 11.26 g tartaric acid (C
4H
6O
8) acetone in mix to settled solution; Then add 0.024 g aluminium oxide Al
2O
3Nano powder; Ultrasonic 0.4 h after vacuum removal bubble is processed 2 h, takes out 80 ℃ and adds thermal agitation, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 1 ℃/min, rises to 550 ℃ of calcining 8h with powder; Continuation rises to 850 ℃ of calcining insulation 8h with the heating rate of 8 ℃/min, obtains manganese silicate of lithium/alumina nano powder composite positive pole.
Embodiment 4
Weighing lithium carbonate Li
2CO
33.6945 g, manganese carbonate MnCO
35.7475 g and tetraethoxysilane (C
8H
20O
4Si) 10.4165 g join 200 ml and are dissolved with 15.009 g tartaric acid (C
4H
6O
8) water in mix to settled solution; Then add 0.032 g zirconia ZrO
2Nano powder; Ultrasonic 0.5 h after vacuum removal bubble is processed 2.5 h, takes out 90 ℃ and adds thermal agitation, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 2 ℃/min, rises to 350 ℃ of calcining 3h with powder; Continuation rises to 850 ℃ of calcining insulation 9h with the heating rate of 3 ℃/min, obtains manganese silicate of lithium/zirconia nano-powder composite positive pole.
Embodiment 5
Weighing lithium chloride LiCl 4.239 g, manganese chloride MnCl
24H
2O 9.8955 g and tetraethoxysilane (C
8H
20O
4Si) 10.4165 g join 200 ml and are dissolved with 24 g citric acid (C
6H
8O
7) water in mix to settled solution; Then add 0.08 g zinc oxide ZnO nano powder; Ultrasonic 0.6 h after vacuum removal bubble is processed 3 h, takes out 100 ℃ and adds thermal agitation, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 2 ℃/min, rises to 450 ℃ of calcining 7h with powder; Continuation rises to 650 ℃ of calcining insulation 10h with the heating rate of 5 ℃/min, obtains manganese silicate of lithium/zinc oxide nano composite positive pole.
Weighing lithium carbonate Li
2CO
33.6945 g, manganese sulfate MnSO
411.153 g and silicon dioxide SiO
23.0045 g joins 230 ml and is dissolved with 26 g citric acid (C
6H
8O
7) water in mix to settled solution; Then add 0.1 g metatitanic acid H
2Ti
3O
7Nano powder; Ultrasonic 0.7 h, vacuum is taken out 110 ℃ and is added thermal agitation after removing bubble processing 3.5h, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 2 ℃/min, rises to 550 ℃ of calcining 2h with powder; Continuation rises to 750 ℃ of calcining insulation 11h with the heating rate of 7 ℃/min, obtains manganese silicate of lithium/metatitanic acid nano powder composite positive pole.
Weighing lithium nitrate LiNO
36.894 g, manganese acetate Mn (Ac)
24H
2O 12.7799 g and tetraethoxysilane (C
8H
20O
4Si) 10.4165 g join 170 ml and are dissolved with 22.52 g tartaric acid (C
4H
6O
8) isopropyl alcohol in mix to settled solution; Then add 0.1448 g titanium dioxide TiO
2Nanotube; Ultrasonic 0.8 h after vacuum removal bubble is processed 4 h, takes out 65 ℃ and adds thermal agitation, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 3 ℃/min, rises to 350 ℃ of calcining 6h with powder; Continuation rises to 750 ℃ of calcining insulation 12h with the heating rate of 2.5 ℃/min, obtains manganese silicate of lithium/titania nanotube composite positive pole.
Weighing lithium acetate LiAc2H
2O 10.202 g, manganese acetate Mn (Ac)
24H
2O 12.7799 g and silicon dioxide SiO
23.0045 g joins 190 ml and is dissolved with 20 g citric acid (C
6H
8O
7) alcohol in mix to settled solution; Then add 0.05 g metatitanic acid H
2Ti
3O
7Nanotube; Ultrasonic 0.9 h, vacuum is taken out 75 ℃ and is added thermal agitation after removing bubble processing 5h, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 3 ℃/min, rises to 450 ℃ of calcining 4h with powder; Continuation rises to 850 ℃ of calcining insulation 13h with the heating rate of 4.5 ℃/min, obtains manganese silicate of lithium/titanate radical nanopipe composite positive pole.
Weighing lithium hydroxide LiOHH
2O 4.195 g, manganese carbonate MnCO
35.7475 g and tetraethoxysilane (C
8H
20O
4Si) 10.4165 g join 210ml and are dissolved with 9.02 g tartaric acid (C
4H
6O
8) water in mix to settled solution; Then add 0.1609 g aluminium oxide Al
2O
3Nano powder; Ultrasonic 1h, vacuum is taken out 120 ℃ and is added thermal agitation after removing bubble processing 6h, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 3 ℃/min, rises to 550 ℃ of calcining 5h with powder; Continuation rises to 650 ℃ of calcining insulation 20h with the heating rate of 6 ℃/min, obtains manganese silicate of lithium/alumina nano powder composite positive pole.
Weighing lithium chloride LiCl 4.239 g, manganese carbonate MnCO
35.7475 g and silicon dioxide SiO
23.0045 g joins 210 ml and is dissolved with 15.4 g citric acid (C
6H
8O
7) alcohol in mix to settled solution; Then add 0.12 g zinc oxide ZnO nano powder; Ultrasonic 0.9 h, vacuum is taken out 70 ℃ and is added thermal agitation after removing bubble processing 5h, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 1.5 ℃/min, rises to 400 ℃ of calcining 5.5h with powder; Continuation rises to 800 ℃ of calcining insulation 10h with the heating rate of 5.5 ℃/min, obtains manganese silicate of lithium/zinc oxide nano composite positive pole.
Weighing lithium nitrate LiNO
36.894 g, manganese chloride MnCl
24H
2O 9.8955 g and tetraethoxysilane (C
8H
20O
4Si) 10.4165 g join 195ml and are dissolved with 17.26 g tartaric acid (C
4H
6O
8) isopropyl alcohol in mix to settled solution; Then add 0.096g metatitanic acid H
2Ti
3O
7Nano powder; Ultrasonic 0.5h, vacuum is taken out 60 ℃ and is added thermal agitation after removing bubble processing 2.5h, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 1.5 ℃/min, rises to 500 ℃ of calcining 5.5h with powder; Continuation rises to 700 ℃ of calcining insulation 12h with the heating rate of 6 ℃/min, obtains manganese silicate of lithium/metatitanic acid nano powder composite positive pole.
Embodiment 12
Weighing lithium hydroxide LiOHH
2O 4.195 g, manganese sulfate MnSO
411.153 g and silicon dioxide SiO
23.0045 g joins 230 ml and is dissolved with 13.7 g citric acid (C
6H
8O
7) acetone in mix to settled solution; Then add 0.16 g zirconia ZrO
2Nano powder; Ultrasonic 1h, vacuum is taken out 65 ℃ and is added thermal agitation after removing bubble processing 1h, obtains gel after the solvent evaporates; The drying and screening refinement under nitrogen atmosphere, with the heating rate of 2.5 ℃/min, rises to 550 ℃ of calcining 8h with powder; Continuation rises to 720 ℃ of calcining insulation 15h with the heating rate of 3.5 ℃/min, obtains manganese silicate of lithium/zirconia nano-powder composite positive pole.
Claims (6)
1. the preparation method of a lithium manganese silicate/nanometer oxide composite anode material, this composite positive pole comprises 98-99.9 wt % manganese silicate of lithium (Li
2MnSiO
4) and the nano-oxide of 0.1-2wt%; It is characterized in that the method utilizes nano-oxide to modify the manganese silicate of lithium electrical property, concrete steps are as follows:
Lithium raw material, manganese raw material and silicon raw material are pressed Li ﹕ Mn ﹕ Si=2 ﹕ 1 ﹕ 1 to be mixed, 0.1～1.5 times the enveloping agent solution that adds the manganese silicate of lithium mole, stirring and dissolving is homogeneous solution, then the nano-oxide that adds manganese silicate of lithium quality 1～5%, stir and ultrasonic processing 0.2～1h, vacuum is taken out 60～120 ℃ of heat treated and stirring after removing bubble processing 1～6h, obtains gel; Refinement after dry, with powder calcination processing in inert atmosphere, calcine technology is step multistage heat treatment, the low-temperature zone heating rate is 1～3 ℃/min, rises to 350～550 ℃, insulation 2～8h; Continue, heating rate is 2～8 ℃/min, rises to 650～850 ℃, and insulation 6～20h obtains lithium manganese silicate/nanometer oxide composite anode material.
2. the preparation method of described lithium manganese silicate/nanometer oxide composite anode material according to claim 1 is characterized in that described lithium raw material is a kind of or its mixture in lithium acetate, Lithium hydroxide monohydrate, lithium carbonate, lithium chloride, the lithium nitrate; Described manganese raw material is a kind of or its mixture of manganese acetate, manganese chloride, manganese carbonate, manganese sulfate; Described silicon raw material is a kind of or its mixture in tetraethoxysilane, the silicon dioxide.
3. the preparation method of described lithium manganese silicate/nanometer oxide composite anode material according to claim 1, it is characterized in that, described nano-oxide is the nano level oxide of powdery, perhaps is the oxide of tubular nanometer level, perhaps is the oxide of the hybrid nanoscale of powdery and tubulose.
4. according to claim 1 or the preparation method of 3 described lithium manganese silicate/nanometer oxide composite anode materials, it is characterized in that, described nano-oxide is selected from: nano alumina powder, nanometer titanium dioxide titanium valve, nano oxidized zirconium powder, nano zinc oxide powder, nano barium titanate powder, nano titanium dioxide pipe or nanotubes of titanic acid, or two or more mixture in them.
5. the preparation method of described lithium manganese silicate/nanometer oxide composite anode material according to claim 1 is characterized in that described complexing agent is selected from citric acid, tartaric acid or its mixture; And be dissolved in a kind of or its mixture in deionized water, ethanol, isopropyl alcohol and the acetone, be made into enveloping agent solution.
6. the preparation method of described lithium manganese silicate/nanometer oxide composite anode material according to claim 1, it is characterized in that, described ultrasonic processing has activated the surface of nano-oxide, manganese silicate of lithium be connected the composite material of oxide and connected by the interface of chemical bonding; Nano-oxide after the described ultrasonic processing activation is distributed in the manganese silicate of lithium particle surface or is embedded in the gap of manganese silicate of lithium particle.
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| CN102340005A (en) * | 2011-10-09 | 2012-02-01 | 上海大学 | Preparation method of lithium manganous silicate/graphene composite lithium ion cathode material |
| CN103682334B (en) * | 2013-12-04 | 2015-10-28 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method of the lithium manganese silicate anode material that a kind of nano zine oxide is coated |
| CN107706396B (en) * | 2017-10-30 | 2020-10-09 | 上海电力学院 | Oxide composite lithium manganese silicate cathode material and preparation method thereof |
| CN111564617B (en) * | 2020-05-18 | 2021-07-16 | 上海锂基新材料科技有限公司 | ZrO (ZrO)2Cladding Al doped Li2MnSiO4Lithium ion battery anode material and preparation method thereof |
| CN113782818A (en) * | 2021-08-18 | 2021-12-10 | 湖南法恩莱特新能源科技有限公司 | Low-temperature-resistant electrolyte and preparation method and application thereof |
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| CN101504994A (en) * | 2009-03-04 | 2009-08-12 | 张贵萍 | Lithium manganese phosphate or lithium manganese silicate power cell, positive and negative pole manufacturing method thereof |
| CN101540393A (en) * | 2009-04-09 | 2009-09-23 | 西安建筑科技大学 | Method for preparing lithium-manganese silicate of lithium-ion battery cathode material |
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| CN101504994A (en) * | 2009-03-04 | 2009-08-12 | 张贵萍 | Lithium manganese phosphate or lithium manganese silicate power cell, positive and negative pole manufacturing method thereof |
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