CN103035901B - Nanometer oxide coated lithium titanate negative electrode material of lithium battery, and preparation method for negative electrode material - Google Patents
Nanometer oxide coated lithium titanate negative electrode material of lithium battery, and preparation method for negative electrode material Download PDFInfo
- Publication number
- CN103035901B CN103035901B CN201210557799.5A CN201210557799A CN103035901B CN 103035901 B CN103035901 B CN 103035901B CN 201210557799 A CN201210557799 A CN 201210557799A CN 103035901 B CN103035901 B CN 103035901B
- Authority
- CN
- China
- Prior art keywords
- oxide
- lithium titanate
- mixed
- lithium
- lithium battery
- 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.)
- Active
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 155
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 154
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title abstract description 34
- 239000007773 negative electrode material Substances 0.000 title abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 38
- 239000004094 surface-active agent Substances 0.000 claims abstract description 36
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000011247 coating layer Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- -1 polyoxyethylene Polymers 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 48
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 40
- 239000010405 anode material Substances 0.000 claims description 32
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 28
- 238000000498 ball milling Methods 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- 239000011787 zinc oxide Substances 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010348 incorporation Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004698 Polyethylene Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 13
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 13
- 239000011268 mixed slurry Substances 0.000 claims description 12
- 229910052810 boron oxide Inorganic materials 0.000 claims description 10
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001451 polypropylene glycol Polymers 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 9
- 239000011118 polyvinyl acetate Substances 0.000 claims description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 7
- 239000004584 polyacrylic acid Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000004800 polyvinyl chloride Substances 0.000 claims description 7
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 24
- 229910001416 lithium ion Inorganic materials 0.000 description 24
- 238000002156 mixing Methods 0.000 description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 16
- 239000002002 slurry Substances 0.000 description 16
- 239000005030 aluminium foil Substances 0.000 description 14
- 238000013461 design Methods 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 7
- 229910001290 LiPF6 Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 238000004513 sizing Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 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
Abstract
The invention relates to a nanometer oxide coated lithium titanate negative electrode material of a lithium battery, and a preparation method for the negative electrode material, and belongs to the technical field of negative electrode materials of lithium batteries. The negative electrode material comprises the following raw materials in percentage by weight: 1 to 10 percent of mixed oxide, 40 to 60 percent of lithium titanate, 1 to 8 percent of binder, 0.5 to 2 percent of surfactant and 20 to 57.5 percent of deionized water. The lithium titanate negative electrode material is used in combination of spherical and rodlike oxides to serve as coating particles; and the formed oxide coating has the characteristic of compact and uniform coating layer and can cover the surfaces of the lithium titanate particles well.
Description
Technical field
The present invention relates to negative material of a kind of lithium battery and preparation method thereof, more particularly, the present invention relates to coated lithium titanate anode material of a kind of lithium battery nano-oxide and preparation method thereof, belong to lithium cell cathode material technical field.
Background technology
At present, the research emphasis of cathode material of lithium ion battery is just towards the motive-power battery material future development of high-energy-density, high charge-discharge efficiencies, high cycle performance and resistance to high power charging-discharging.Business-like cathode material of lithium ion battery is all Carbon anode mostly now, but there are some defects in carbon negative pole material, as: generate SEI film (solid electrolyte film) first in discharge process, cause irreversible capacity loss, high temperature may cause cell panel lost efficacy or caused safety issue, high rate during charging-discharging is poor, and these problems make this material can not meet the demand of high-efficiency battery especially electrokinetic cell.
Compared with Carbon anode, spinel type lithium titanate (Li
4ti
5o
12) material has lot of advantages, as: 1) have higher solid phase ion conductivity, thus have good rapid charge characteristic, 10C charging capacity is greater than 80%DOD(depth of discharge); 2) lithium titanate material does not need performance SEI film in battery first charge-discharge process, therefore has higher energy conversion efficiency; 3) lithium titanate material does not form lithium metal or alloy in charging process, has higher fail safe; 4) lithium titanate material crystal structure in cyclic process is stablized, and has good cyclical stability.Therefore lithium titanate material can be used as the good negative material of lithium-ion-power cell, is the focus of current lithium ion battery negative material research, is also the popular object of design power battery for hybrid electric vehicle.
But lithium titanate also has the feature that particle size is little, specific area large, water absorption is stronger.Conventional oxide coating is all near-sphericals, and covered effect is poor, can not by lithium titanate densification parcel.In cell manufacturing process, ambient moisture is difficult to again control, and causes inside battery moisture too high.And then cause chain electrochemical reaction, promote electrolyte decomposition, and discharge a large amount of gas.Particularly lithium titanate battery is after high-temperature storage, and inside battery can assemble a large amount of gas, and the swelling of battery clearly, seriously constrains the performance of battery performance.
It is 201110204060.1 that State Intellectual Property Office discloses an application number in 2011.12.28, name is called the patent of invention of " negative electrode active material and preparation method thereof and the lithium rechargeable battery adopting this negative electrode active material to prepare ", the lithium rechargeable battery that this patent provides a kind of negative electrode active material and preparation method thereof and adopts this negative electrode active material to prepare: spherical oxide and bar-shaped oxide are mixed to get mixed oxide, mixed oxide is put into the 1-METHYLPYRROLIDONE solution ball milling mixing 1h that mass fraction is the polyvinylidene fluoride of 4%, and then add lithium titanate and ball milling mixing 3h obtains slurry, slurry heating is stirred to dry titanium composite in 170 DEG C, titanium composite is being passed into Ar or N
2or in 600 DEG C of baking 24-72h under vacuum, be down to room temperature after baking and obtain negative electrode active material, the negative electrode active material formed has the fine and close and uniform feature of coating layer, effectively can reduce the contact of lithium titanate and moisture, particle size due to oxide is nanoscale, effectively lithium titanate can be wrapped up, avoid the generation of ballooning to greatest extent, be conducive to the cycle life of raising lithium rechargeable battery, storge quality and fail safe.
In above-mentioned patent, solvent is 1-METHYLPYRROLIDONE solution, is organic system, and cost is high, not environmentally; Binding agent adopts fluorine system binding agent and polyvinylidene fluoride, and cost is high, not environmentally, and cause electrode slurry the stability even stability of battery not high; In addition, it is low also to there is electrode slurry solid content in above-mentioned patent, the problem that stability and consistency are not good.
Summary of the invention
The present invention is intended to solve in prior art, lithium titanate anode material causes battery inflatable, and cost is high, not environmentally in documents, the problem that electrode, stability test and consistency are not good, provides a kind of lithium battery nano-oxide coated lithium titanate anode material, solves battery inflatable problem, extend battery life, improve fail safe, and cost is low, environmental protection, stability and consistency good.
Another object of the present invention is for providing the optimized fabrication method of the coated lithium titanate anode material of a kind of above-mentioned lithium battery nano-oxide.
In order to realize foregoing invention object, its concrete technical scheme is as follows:
The coated lithium titanate anode material of a kind of lithium battery nano-oxide, is characterized in that: comprise the following raw material components according to weight percent meter:
Mixed oxide 1-10%
Lithium titanate 40-60%
Aqueous binders 1-8%
Surfactant 0.5-2%
Deionized water 20-57.5%;
Described mixed oxide is bar-shaped oxide and spherical oxide, and mixed oxide is that coating layer is coated on lithium titanate surface;
Described surfactant is a kind of in polyoxyethylene one polyoxypropylene polymer, polyvinylpyrrolidone, polyoxyethylene aliphatic alcohol ether and polyoxyethylene fatty acid ester or arbitrary proportion multiple.
The present invention is preferred, and described bar-shaped oxide is zirconia, silica, calcium oxide.
The present invention is preferred, and described spherical oxide is zinc oxide, boron oxide.
The present invention is preferred, and in described mixed oxide, the mass fraction of bar-shaped oxide is 5-95%.
The present invention is preferred, and the aspect ratio of described bar-shaped oxide is 2-10, and the particle diameter of described spherical oxide and the longest edge of bar-shaped oxide are 0.005-10 μm.
The present invention is preferred, and described aqueous binders is the multiple of a kind of or arbitrary proportion in polyethylene nitrile (PAN), polyvinyl chloride (PVC), polyvinyl acetate (PVAC), polyacrylic acid glycol ester (PEGDA) and polymethyl methacrylate (PMMA).
A preparation method for the coated lithium titanate anode material of lithium battery nano-oxide, is characterized in that: comprise following processing step:
A, spherical oxide and bar-shaped oxide are mixed to get mixed oxide, described incorporation time is 1-3h;
B, mixed oxide steps A obtained put into aqueous binders, and ball milling mixes, and obtains mixture, and described incorporation time is 1-3h;
Add lithium titanate and surfactant in C, the mixture that obtains to step B, and ball milling is mixed to get mixed slurry, described incorporation time is 3-5h;
D, above-mentioned mixed slurry heated and be stirred to drying at 100-200 DEG C obtain titanium composite;
E, the titanium composite obtained by step D are passing into Ar, N
2or in 500-700 DEG C of baking 24-72h under vacuum, be down to room temperature after baking and obtain the coated lithium titanate anode material of lithium battery nano-oxide.
Negative electrode active material prepared by the preparation method of described negative electrode active material, comprises lithium titanate and is coated on the oxide cladding layers on lithium titanate surface.
Described oxide cladding layers forms by second particle that is spherical or near-spherical, and the particle diameter of second particle is 0.05-10 μm (remarks: the diameter of primary particle is 10-100nm).
The particle diameter of described lithium titanate is less than or equal to 5 μm.
A kind of lithium battery adopting the coated lithium titanate anode material of above-mentioned lithium battery nano-oxide to make.
The Advantageous Effects that the present invention brings:
1, lithium titanate anode material of the present invention adopt the oxide of spherical and bar-shaped two kinds of shapes as coated particle with the use of, the oxide coating formed has the fine and close and uniform feature of coating layer, can better cover lithium titanate particle surface;
2, the present invention is by the oxide coating in the densification of lithium titanate Surface coating one deck, effectively can reduce the contact of lithium titanate and moisture; Particle size due to oxide is nanoscale, effectively can be wrapped up by lithium titanate, can reduce the reaction of lithium titanate and moisture and electrolyte simultaneously; In addition, because nano level oxide has nano effect, a large amount of gas can be adsorbed, effectively reduce the content of free gas, avoid the generation of ballooning to greatest extent, be conducive to the cycle life of raising lithium rechargeable battery, storge quality and fail safe;
3, lithium titanate anode composition of the present invention is relative to documents, for water-based system, there is the feature of safety, environmental protection and low cost, be particularly suitable for suitability for industrialized production, and the preferred binding agent of the present invention also can bring the effect of environmental protection and low cost, the stability that electrode slurry is good, can improve the stability of battery further;
4, the surfactant that adds of the present invention, makes electrode slurry have higher solid content, preferably stability and consistency, can improve battery with two side terminals further.
Embodiment
embodiment 1
The coated lithium titanate anode material of a kind of lithium battery nano-oxide, comprises the following raw material components according to weight percent meter:
Mixed oxide 1%
Lithium titanate 40%
Aqueous binders 8%
Surfactant 2%
Deionized water 49%;
Described mixed oxide is bar-shaped oxide and spherical oxide, and mixed oxide is that coating layer is coated on lithium titanate surface;
Described surfactant is a kind of in polyoxyethylene one polyoxypropylene polymer, polyvinylpyrrolidone, polyoxyethylene aliphatic alcohol ether and polyoxyethylene fatty acid ester or arbitrary proportion multiple.
embodiment 2
The coated lithium titanate anode material of a kind of lithium battery nano-oxide, comprises the following raw material components according to weight percent meter:
Mixed oxide 10%
Lithium titanate 60%
Aqueous binders 1%
Surfactant 0.5%
Deionized water 28.5%;
Described mixed oxide is bar-shaped oxide and spherical oxide, and mixed oxide is that coating layer is coated on lithium titanate surface;
Described surfactant is a kind of in polyoxyethylene one polyoxypropylene polymer, polyvinylpyrrolidone, polyoxyethylene aliphatic alcohol ether and polyoxyethylene fatty acid ester or arbitrary proportion multiple.
embodiment 3
The coated lithium titanate anode material of a kind of lithium battery nano-oxide, comprises the following raw material components according to weight percent meter:
Mixed oxide 10%
Lithium titanate 60%
Aqueous binders 8%
Surfactant 2%
Deionized water 20%;
Described mixed oxide is bar-shaped oxide and spherical oxide, and mixed oxide is that coating layer is coated on lithium titanate surface;
Described surfactant is a kind of in polyoxyethylene one polyoxypropylene polymer, polyvinylpyrrolidone, polyoxyethylene aliphatic alcohol ether and polyoxyethylene fatty acid ester or arbitrary proportion multiple.
embodiment 4
The coated lithium titanate anode material of a kind of lithium battery nano-oxide, comprises the following raw material components according to weight percent meter:
Mixed oxide 1%
Lithium titanate 40%
Aqueous binders 1%
Surfactant 0.5%
Deionized water 57.5%;
Described mixed oxide is bar-shaped oxide and spherical oxide, and mixed oxide is that coating layer is coated on lithium titanate surface;
Described surfactant is a kind of in polyoxyethylene one polyoxypropylene polymer, polyvinylpyrrolidone, polyoxyethylene aliphatic alcohol ether and polyoxyethylene fatty acid ester or arbitrary proportion multiple.
embodiment 5
The coated lithium titanate anode material of a kind of lithium battery nano-oxide, comprises the following raw material components according to weight percent meter:
Mixed oxide 5%
Lithium titanate 50%
Aqueous binders 5%
Surfactant 1%
Deionized water 39%;
Described mixed oxide is bar-shaped oxide and spherical oxide, and mixed oxide is that coating layer is coated on lithium titanate surface;
Described surfactant is a kind of in polyoxyethylene one polyoxypropylene polymer, polyvinylpyrrolidone, polyoxyethylene aliphatic alcohol ether and polyoxyethylene fatty acid ester or arbitrary proportion multiple.
embodiment 6
On the basis of embodiment 1-5, preferred:
Described bar-shaped oxide is zirconia, silica, calcium oxide.
Described spherical oxide is zinc oxide, boron oxide.
In described mixed oxide, the mass fraction of bar-shaped oxide is 5%.
The aspect ratio of described bar-shaped oxide is 2, and the particle diameter of described spherical oxide and the longest edge of bar-shaped oxide are 0.005 μm.
Described aqueous binders is the multiple of a kind of or arbitrary proportion in polyethylene nitrile, polyvinyl chloride, polyvinyl acetate, polyacrylic acid glycol ester and polymethyl methacrylate.
embodiment 7
On the basis of embodiment 1-5, preferred:
Described bar-shaped oxide is zirconia, silica, calcium oxide.
Described spherical oxide is zinc oxide, boron oxide.
In described mixed oxide, the mass fraction of bar-shaped oxide is 95%.
The aspect ratio of described bar-shaped oxide is 10, and the particle diameter of described spherical oxide and the longest edge of bar-shaped oxide are 10 μm.
Described aqueous binders is the multiple of a kind of or arbitrary proportion in polyethylene nitrile, polyvinyl chloride, polyvinyl acetate, polyacrylic acid glycol ester and polymethyl methacrylate.
embodiment 8
On the basis of embodiment 1-5, preferred:
Described bar-shaped oxide is zirconia, silica, calcium oxide.
Described spherical oxide is zinc oxide, boron oxide.
In described mixed oxide, the mass fraction of bar-shaped oxide is 50%.
The aspect ratio of described bar-shaped oxide is 6, and the particle diameter of described spherical oxide and the longest edge of bar-shaped oxide are 5 μm.
Described aqueous binders is the multiple of a kind of or arbitrary proportion in polyethylene nitrile, polyvinyl chloride, polyvinyl acetate, polyacrylic acid glycol ester and polymethyl methacrylate.
embodiment 9
On the basis of embodiment 1-5, preferred:
Described bar-shaped oxide is zirconia, silica, calcium oxide.
Described spherical oxide is zinc oxide, boron oxide.
In described mixed oxide, the mass fraction of bar-shaped oxide is 21%.
The aspect ratio of described bar-shaped oxide is 8, and the particle diameter of described spherical oxide and the longest edge of bar-shaped oxide are 2.5 μm.
Described aqueous binders is the multiple of a kind of or arbitrary proportion in polyethylene nitrile, polyvinyl chloride, polyvinyl acetate, polyacrylic acid glycol ester and polymethyl methacrylate.
embodiment 10
A preparation method for the coated lithium titanate anode material of lithium battery nano-oxide, comprises following processing step:
A, spherical oxide and bar-shaped oxide are mixed to get mixed oxide, described incorporation time is 1h;
B, mixed oxide steps A obtained put into aqueous binders, and ball milling mixes, and obtains mixture, and described incorporation time is 1h;
Add lithium titanate and surfactant in C, the mixture that obtains to step B, and ball milling is mixed to get mixed slurry, described incorporation time is 3h;
D, above-mentioned mixed slurry heated and be stirred to drying at 100 DEG C obtain titanium composite;
E, the titanium composite obtained by step D are passing into Ar, N
2or in 500 DEG C of baking 24h under vacuum, be down to room temperature after baking and obtain the coated lithium titanate anode material of lithium battery nano-oxide.
embodiment 11
A preparation method for the coated lithium titanate anode material of lithium battery nano-oxide, comprises following processing step:
A, spherical oxide and bar-shaped oxide are mixed to get mixed oxide, described incorporation time is 3h;
B, mixed oxide steps A obtained put into aqueous binders, and ball milling mixes, and obtains mixture, and described incorporation time is 3h;
Add lithium titanate and surfactant in C, the mixture that obtains to step B, and ball milling is mixed to get mixed slurry, described incorporation time is 5h;
D, above-mentioned mixed slurry heated and be stirred to drying at 200 DEG C obtain titanium composite;
E, the titanium composite obtained by step D are passing into Ar, N
2or in 700 DEG C of baking 72h under vacuum, be down to room temperature after baking and obtain the coated lithium titanate anode material of lithium battery nano-oxide.
embodiment 12
A preparation method for the coated lithium titanate anode material of lithium battery nano-oxide, comprises following processing step:
A, spherical oxide and bar-shaped oxide are mixed to get mixed oxide, described incorporation time is 2h;
B, mixed oxide steps A obtained put into aqueous binders, and ball milling mixes, and obtains mixture, and described incorporation time is 2h;
Add lithium titanate and surfactant in C, the mixture that obtains to step B, and ball milling is mixed to get mixed slurry, described incorporation time is 4h;
D, above-mentioned mixed slurry heated and be stirred to drying at 150 DEG C obtain titanium composite;
E, the titanium composite obtained by step D are passing into Ar, N
2or in 600 DEG C of baking 48h under vacuum, be down to room temperature after baking and obtain the coated lithium titanate anode material of lithium battery nano-oxide.
embodiment 13
A preparation method for the coated lithium titanate anode material of lithium battery nano-oxide, comprises following processing step:
A, spherical oxide and bar-shaped oxide are mixed to get mixed oxide, described incorporation time is 2.5h;
B, mixed oxide steps A obtained put into aqueous binders, and ball milling mixes, and obtains mixture, and described incorporation time is 1.5h;
Add lithium titanate and surfactant in C, the mixture that obtains to step B, and ball milling is mixed to get mixed slurry, described incorporation time is 3.5h;
D, above-mentioned mixed slurry heated and be stirred to drying at 100-200 DEG C obtain titanium composite;
E, the titanium composite obtained by step D are passing into Ar, N
2or in 550 DEG C of baking 30h under vacuum, be down to room temperature after baking and obtain the coated lithium titanate anode material of lithium battery nano-oxide.
embodiment 14
Cathode composition and preparation thereof: to be first the spherical alumina of 10nm and aspect ratio by particle diameter be 6 zinc oxide mixing 1h obtain mixed oxide, the aqueous solution ball milling mixing 1h of the polyethylene nitrile that mixed oxide is put into, and then add particle diameter and be the lithium titanate of 5 μm and surfactant polyoxyethylene one polyoxypropylene polymer and ball milling mixing 3h obtains slurry, slurry is heated and is stirred to sample drying in 170 DEG C and obtains titanium composite, titanium composite is being passed into Ar or N
2or in 600 DEG C of baking 24h under vacuum, be down to room temperature after baking and obtain cathode composition.Described aluminium oxide: zinc oxide: lithium titanate: aqueous binders: surfactant: deionized water=0.5:0.5:40:1:0.5:20.
Negative pole: by the one side dressing on the aluminium foil of 10 microns of the cathode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.2mAh/cm2.
Positive pole: prepare anode sizing agent one side dressing on the aluminium foil of 12 microns with cobalt acid lithium material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm2.
Lithium ion battery: with the positive pole obtained by said method and negative pole, the PE perforated membrane of 20 microns is barrier film, dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution of 1M LiPF6, as electrolyte, becomes design capacity to be the Soft Roll polymer battery of 800mAh by fabrication techniques known in those skilled in the art in humidity-controlled glove box.
Comparative example 1:
Cathode composition and preparation thereof: adopt method known in those skilled in the art to prepare cathode composition, in 1-METHYLPYRROLIDONE, be mixed with into suspension in (NMP) with polyvinylidene fluoride by lithium titanate material.
Negative pole: prepare negative pole according to the method described above.
Positive pole: prepare positive pole according to the method described above.
Lithium ion battery: prepare lithium ion battery according to the method described above.
embodiment 15
Cathode composition and preparation thereof: to be first the spherical silicon dioxide of 50nm and aspect ratio by particle diameter be 8 zinc oxide mixing 3h obtain mixed oxide, mixed oxide is put into the aqueous solution ball milling mixing 3h of polyvinyl chloride (PVC), and then add particle diameter and be the lithium titanate of 5 μm and surfactant polyvinylpyrrolidone and ball milling mixing 3h obtains slurry, slurry is heated and is stirred to sample drying in 170 DEG C and obtains titanium composite, titanium composite is being passed into Ar or N
2or in 600 DEG C of baking 24h under vacuum, be down to room temperature after baking and obtain cathode composition.Described silicon dioxide: zinc oxide: lithium titanate: aqueous binders: surfactant: deionized water=5:5:60:1:0.5:57.5.
Negative pole: by the one side dressing on the aluminium foil of 10 microns of the cathode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.2mAh/cm2.
Positive pole: prepare anode sizing agent one side dressing on the aluminium foil of 12 microns with cobalt acid lithium material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm2.
Lithium ion battery: with the positive pole obtained by said method and negative pole, the PE perforated membrane of 20 microns is barrier film, dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution of 1M LiPF6, as electrolyte, becomes design capacity to be the Soft Roll polymer battery of 800mAh by fabrication techniques known in those skilled in the art in humidity-controlled glove box.
Comparative example 2:
Cathode composition and preparation thereof: adopt method known in those skilled in the art to prepare cathode composition, in 1-METHYLPYRROLIDONE, be mixed with into suspension in (NMP) with polyvinylidene fluoride by lithium titanate material.
Negative pole: prepare negative pole according to the method described above.
Positive pole: prepare positive pole according to the method described above.
Lithium ion battery: prepare lithium ion battery according to the method described above.
embodiment 16
Cathode composition and preparation thereof: to be first the spherical calcium oxide of 20nm and aspect ratio by particle diameter be 10 zinc oxide mixing 3h obtain mixed oxide, mixed oxide is put into the aqueous solution ball milling mixing 3h of polymethyl methacrylate (PMMA), and then add particle diameter and be the lithium titanate of 5 μm and surfactant polyoxyethylene fatty alcohol ether and ball milling mixing 3h obtains slurry, slurry is heated and is stirred to sample drying in 170 DEG C and obtains titanium composite, titanium composite is being passed into Ar or N
2or in 600 DEG C of baking 24h under vacuum, be down to room temperature after baking and obtain cathode composition.Described calcium oxide: zinc oxide: lithium titanate: aqueous binders: surfactant: deionized water=3:2:50:4:1:40.
Negative pole: by the one side dressing on the aluminium foil of 10 microns of the cathode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.2mAh/cm2.
Positive pole: prepare anode sizing agent one side dressing on the aluminium foil of 12 microns with cobalt acid lithium material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm2.
Lithium ion battery: with the positive pole obtained by said method and negative pole, the PE perforated membrane of 20 microns is barrier film, dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution of 1M LiPF6, as electrolyte, becomes design capacity to be the Soft Roll polymer battery of 800mAh by fabrication techniques known in those skilled in the art in humidity-controlled glove box.
Comparative example 3:
Cathode composition and preparation thereof: adopt method known in those skilled in the art to prepare cathode composition, in 1-METHYLPYRROLIDONE, be mixed with into suspension in (NMP) with polyvinylidene fluoride by lithium titanate material.
Negative pole: prepare negative pole according to the method described above.
Positive pole: prepare positive pole according to the method described above.
Lithium ion battery: prepare lithium ion battery according to the method described above.
embodiment 17
Cathode composition and preparation thereof: to be first the spherical titanium oxide of 20nm and aspect ratio by particle diameter be 2 zinc oxide mixing 3h obtain mixed oxide, mixed oxide is put into the aqueous solution ball milling mixing 3h of polymethyl methacrylate (PMMA), and then add lithium titanate and the surfactant polyoxyethylene fatty acid ester that particle diameter is 5 μm, and ball milling mixing 3h obtains slurry, slurry is heated and is stirred to sample drying in 170 DEG C and obtains titanium composite, titanium composite is being passed into Ar or N
2or in 600 DEG C of baking 24h under vacuum, be down to room temperature after baking and obtain cathode composition.Described titanium oxide: zinc oxide: lithium titanate: aqueous binders: surfactant: deionized water=3:2:55:4:1:35.
Negative pole: by the one side dressing on the aluminium foil of 10 microns of the cathode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.2mAh/cm2.
Positive pole: prepare anode sizing agent one side dressing on the aluminium foil of 12 microns with cobalt acid lithium material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm2.
Lithium ion battery: with the positive pole obtained by said method and negative pole, the PE perforated membrane of 20 microns is barrier film, dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution of 1M LiPF6, as electrolyte, becomes design capacity to be the Soft Roll polymer battery of 800mAh by fabrication techniques known in those skilled in the art in humidity-controlled glove box.
Comparative example 4:
Cathode composition and preparation thereof: adopt method known in those skilled in the art to prepare cathode composition, in 1-METHYLPYRROLIDONE, be mixed with into suspension in (NMP) with polyvinylidene fluoride by lithium titanate material.
Negative pole: prepare negative pole according to the method described above.
Positive pole: prepare positive pole according to the method described above.
Lithium ion battery: prepare lithium ion battery according to the method described above.
embodiment 18
Cathode composition and preparation thereof: to be first the spherical boron oxide of 20nm and aspect ratio by particle diameter be 10 zinc oxide mixing 3h obtain mixed oxide, mixed oxide is put into the aqueous solution ball milling mixing 3h of polymethyl methacrylate (PMMA), and then add particle diameter and be the lithium titanate of 5 μm and surfactant * * * and ball milling mixing 3h obtains slurry, slurry is heated and is stirred to sample drying in 170 DEG C and obtains titanium composite, titanium composite is being passed into Ar or N
2or in 600 DEG C of baking 24h under vacuum, be down to room temperature after baking and obtain cathode composition.Described boron oxide: zinc oxide: lithium titanate: aqueous binders: surfactant: deionized water=3:2:55:4:1:35.
Negative pole: by the one side dressing on the aluminium foil of 10 microns of the cathode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.2mAh/cm2.
Positive pole: prepare anode sizing agent one side dressing on the aluminium foil of 12 microns with cobalt acid lithium material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm2.
Lithium ion battery: with the positive pole obtained by said method and negative pole, the PE perforated membrane of 20 microns is barrier film, dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution of 1M LiPF6, as electrolyte, becomes design capacity to be the Soft Roll polymer battery of 800mAh by fabrication techniques known in those skilled in the art in humidity-controlled glove box.
Comparative example 5:
Cathode composition and preparation thereof: adopt method known in those skilled in the art to prepare cathode composition, in 1-METHYLPYRROLIDONE, be mixed with into suspension in (NMP) with polyvinylidene fluoride by lithium titanate material.
Negative pole: prepare negative pole according to the method described above.
Positive pole: prepare positive pole according to the method described above.
Lithium ion battery: prepare lithium ion battery according to the method described above.
embodiment 19
Cathode composition and preparation thereof: to be first the spherical boron oxide of 20nm and aspect ratio by particle diameter be 10 zinc oxide mixing 3h obtain mixed oxide, mixed oxide is put into the aqueous solution ball milling mixing 3h of polyvinyl acetate (PVAC), and then add particle diameter and be the lithium titanate of 5 μm and surfactant polyvinylpyrrolidone and ball milling mixing 3h obtains slurry, slurry is heated and is stirred to sample drying in 170 DEG C and obtains titanium composite, titanium composite is being passed into Ar or N
2or in 600 DEG C of baking 24h under vacuum, be down to room temperature after baking and obtain cathode composition.Described boron oxide: zinc oxide: lithium titanate: aqueous binders: surfactant: deionized water=3:2:55:4:1:35.
Polyoxyethylene one polyoxypropylene polymer, polyvinylpyrrolidone, polyoxyethylene aliphatic alcohol ether, polyoxyethylene fatty acid ester
Negative pole: by the one side dressing on the aluminium foil of 10 microns of the cathode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.2mAh/cm2.
Positive pole: prepare anode sizing agent one side dressing on the aluminium foil of 12 microns with cobalt acid lithium material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm2.
Lithium ion battery: with the positive pole obtained by said method and negative pole, the PE perforated membrane of 20 microns is barrier film, dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution of 1M LiPF6, as electrolyte, becomes design capacity to be the Soft Roll polymer battery of 800mAh by fabrication techniques known in those skilled in the art in humidity-controlled glove box.
Comparative example 6:
Cathode composition and preparation thereof: adopt method known in those skilled in the art to prepare cathode composition, in 1-METHYLPYRROLIDONE, be mixed with into suspension in (NMP) with polyvinylidene fluoride by lithium titanate material.
Negative pole: prepare negative pole according to the method described above.
Positive pole: prepare positive pole according to the method described above.
Lithium ion battery: prepare lithium ion battery according to the method described above.
embodiment 20
Cathode composition and preparation thereof: to be first the Zirconia ball of 20nm and aspect ratio by particle diameter be 6 zinc oxide mixing 3h obtain mixed oxide, mixed oxide is put into the aqueous solution ball milling mixing 3h that mass fraction is the polyacrylic acid glycol ester (PEGDA) of 5%, and then add particle diameter and be the lithium titanate of 5 μm and surfactant polyoxyethylene one polyoxypropylene polymer and ball milling mixing 3h obtains slurry, slurry is heated and is stirred to sample drying in 170 DEG C and obtains titanium composite, titanium composite is being passed into Ar or N
2or in 600 DEG C of baking 24h under vacuum, be down to room temperature after baking and obtain cathode composition.Described zirconia: zinc oxide: lithium titanate: aqueous binders: surfactant: deionized water=3:2:50:6:1:38.
Negative pole: by the one side dressing on the aluminium foil of 10 microns of the cathode composition of above-mentioned preparation; Under 90 DEG C of conditions, vacuum bakeout 3.5h(vacuum degree is-90kPa), roll, cut into slices; The energy density of gained positive pole is 1.2mAh/cm2.
Positive pole: prepare anode sizing agent one side dressing on the aluminium foil of 12 microns with cobalt acid lithium material, vacuum bakeout 3.5h(vacuum degree is-90kPa under 90 DEG C of conditions), roll, cut into slices; The energy density of gained negative pole is 1.4mAh/cm2.
Lithium ion battery: with the positive pole obtained by said method and negative pole, the PE perforated membrane of 20 microns is barrier film, dimethyl carbonate (DMC)/methyl ethyl carbonate (EMC)/vinyl carbonate (EC) (volume ratio 1/1/1) solution of 1M LiPF6, as electrolyte, becomes design capacity to be the Soft Roll polymer battery of 800mAh by fabrication techniques known in those skilled in the art in humidity-controlled glove box.
Comparative example 7:
Cathode composition and preparation thereof: adopt method known in those skilled in the art to prepare cathode composition, in 1-METHYLPYRROLIDONE, be mixed with into suspension in (NMP) with polyvinylidene fluoride by lithium titanate material.
Negative pole: prepare negative pole according to the method described above.
Positive pole: prepare positive pole according to the method described above.
Lithium ion battery: prepare lithium ion battery according to the method described above.
embodiment 21
Performance evaluation
Because nano-oxide particles is tiny, specific area is large, and surface energy is large, is in energy labile state.Distance between nano particle is extremely short, Van der Waals force is each other larger, between particle, the effect etc. of surperficial hydrogen bond, chemical bond acts on and nano particle all can be made to trend towards flocking together, be easy to the second particle forming reunion shape, be deposited on lithium titanate surface, cause lithium titanate roll cover imperfect.Meanwhile, the particle of lithium titanate is comparatively large, and the active force between lithium titanate and nano-oxide particles is also comparatively large, is easy to adsorb nano-oxide.In addition, under the effect of binding agent, the active force between lithium titanate and nano-oxide particles have also been obtained reinforcement.In order to suitably reduce the attraction between nano particle, patent of the present invention adds a certain proportion of rod-shpaed particle in the nano particle of near-spherical, by certain space steric effect, reduce the attraction between nano particle, reduce the reunion between nano particle, make the complete densification of lithium titanate roll cover.
1,60 DEG C of storge quality tests
At room temperature, with design capacity 1C
0the constant current of mA/2.5V and constant voltage are charged, when electric current is less than 0.05C to P1 ~ P5 and Q1 ~ Q3 battery
0charge cutoff during mA.After shelving 30min, with 1C
0the constant current of mA is discharged to 1.2V, measures the initial capacity of battery, thickness and internal resistance.Again with design capacity 1C
0the constant current of mA/2.5V and constant voltage are charged, when electric current is less than 0.05C to P1 ~ P5 and Q1 ~ Q3 battery
0charge cutoff during mA.Battery is placed in the insulating box of 60 DEG C, after shelving 7 days, with 1C
0the constant current of mA is discharged to 1.2V, measures the battery capacity after storing, thickness and internal resistance.
Capacity/initial capacity × 100% after capacity surplus ratio=storage
Internal resistance change=store rear internal resistance-initial internal resistance
Table 1 60 DEG C of storge quality results
2, hot case test
At room temperature, with design capacity 1C
0the constant current of mA/2.5V and constant voltage are charged, when electric current is less than 0.05C to P1 ~ P5 and Q1 ~ Q3 battery
0charge cutoff during mA, after shelving 30min.Deposit 1h under battery being placed in the high temperature of 150 DEG C, 160 DEG C, 170 DEG C, then detect.Result is presented at table 2.
The hot case result of the test (zero: pass through of table 2; ×: do not pass through)
The battery performance prepared of negative electrode active material of the present invention is excellent as can be seen from Table 1 and Table 2, well solves the problem that gas expansion in use occurs battery.Meanwhile, coated by lithium titanate, effectively reduces the contact of lithium titanate and electrolyte, and when reducing abuse, the danger of both positive and negative polarity contact short circuit, improves the fail safe of battery, meet battery to raw-material requirement.
Claims (7)
1. the coated lithium titanate anode material of lithium battery nano-oxide, is characterized in that: comprise the following raw material components according to weight percent meter:
Mixed oxide 1-10%
Lithium titanate 40-60%
Aqueous binders 1-8%
Surfactant 0.5-2%
Deionized water 20-57.5%;
Described mixed oxide is bar-shaped oxide and spherical oxide, and mixed oxide is that coating layer is coated on lithium titanate surface;
Described surfactant is a kind of in polyoxyethylene one polyoxypropylene polymer, polyvinylpyrrolidone, polyoxyethylene aliphatic alcohol ether and polyoxyethylene fatty acid ester or arbitrary proportion multiple;
The described coated lithium titanate anode material of lithium battery nano-oxide is obtained by following methods:
A, spherical oxide and bar-shaped oxide are mixed to get mixed oxide, described incorporation time is 3h;
B, mixed oxide steps A obtained put into aqueous binders, and ball milling mixes, and obtains mixture, and described incorporation time is 3h;
Add lithium titanate and surfactant in C, the mixture that obtains to step B, and ball milling is mixed to get mixed slurry, described incorporation time is 5h;
D, above-mentioned mixed slurry heated and be stirred to drying at 200 DEG C obtain titanium composite;
E, the titanium composite obtained by step D are passing into Ar, N
2or in 700 DEG C of baking 72h under vacuum, be down to room temperature after baking and obtain the coated lithium titanate anode material of lithium battery nano-oxide.
2. the coated lithium titanate anode material of a kind of lithium battery nano-oxide according to claim 1, is characterized in that: described bar-shaped oxide is zirconia, silica, calcium oxide.
3. the coated lithium titanate anode material of a kind of lithium battery nano-oxide according to claim 1 and 2, is characterized in that: described spherical oxide is zinc oxide, boron oxide.
4. the coated lithium titanate anode material of a kind of lithium battery nano-oxide according to claim 1, is characterized in that: in described mixed oxide, the mass fraction of bar-shaped oxide is 5-95%.
5. the coated lithium titanate anode material of a kind of lithium battery nano-oxide according to claim 1, it is characterized in that: the aspect ratio of described bar-shaped oxide is 2-10, the particle diameter of described spherical oxide and the longest edge of bar-shaped oxide are 0.005-10 μm.
6. the coated lithium titanate anode material of a kind of lithium battery nano-oxide according to claim 1, is characterized in that: described aqueous binders is the multiple of a kind of or arbitrary proportion in polyethylene nitrile, polyvinyl chloride, polyvinyl acetate, polyacrylic acid glycol ester and polymethyl methacrylate.
7. the lithium battery adopting the coated lithium titanate anode material of lithium battery nano-oxide as claimed in claim 1 to make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210557799.5A CN103035901B (en) | 2012-12-20 | 2012-12-20 | Nanometer oxide coated lithium titanate negative electrode material of lithium battery, and preparation method for negative electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210557799.5A CN103035901B (en) | 2012-12-20 | 2012-12-20 | Nanometer oxide coated lithium titanate negative electrode material of lithium battery, and preparation method for negative electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103035901A CN103035901A (en) | 2013-04-10 |
| CN103035901B true CN103035901B (en) | 2015-02-04 |
Family
ID=48022564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210557799.5A Active CN103035901B (en) | 2012-12-20 | 2012-12-20 | Nanometer oxide coated lithium titanate negative electrode material of lithium battery, and preparation method for negative electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103035901B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104733720A (en) * | 2015-04-15 | 2015-06-24 | 田东 | Preparation method for modified lithium titanate cathode materials |
| CN104966822A (en) * | 2015-06-16 | 2015-10-07 | 东莞市翔丰华电池材料有限公司 | Multilayer coated lithium titanate cathode material of lithium ion battery and preparation method of multilayer coated lithium titanate cathode material |
| CN105336939B (en) * | 2015-09-30 | 2018-06-15 | 中国科学院过程工程研究所 | Coating modification method of lithium titanate and lithium ion battery thereof |
| CN108187606B (en) * | 2018-01-22 | 2020-07-17 | 天津市职业大学 | Conductive titanium lithium ion sieve and preparation method thereof |
| EP3544095B1 (en) * | 2018-03-22 | 2023-07-26 | Kabushiki Kaisha Toshiba | Secondary battery, battery pack, vehicle, and stationary power supply |
| CN108550831A (en) * | 2018-05-15 | 2018-09-18 | 肇庆益晟商贸有限公司 | A kind of lithium battery negative material and preparation method thereof |
| CN111554907B (en) * | 2020-05-15 | 2022-08-05 | 深圳澳睿新能源科技有限公司 | Application of fatty acid in preparation of lithium ion battery and method for preparing electrode material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101764209A (en) * | 2010-01-04 | 2010-06-30 | 苏州星恒电源有限公司 | Lithium titanate composite electrode material with surface coating layer |
| CN102299311B (en) * | 2011-07-20 | 2013-11-20 | 彩虹集团公司 | Cathode active material and preparation method thereof and lithium ion secondary battery prepared by cathode active material |
| CN102299313A (en) * | 2011-08-10 | 2011-12-28 | 东莞市迈科科技有限公司 | Preparation method of spinel-type lithium titanate |
| CN102376947B (en) * | 2011-10-26 | 2013-03-27 | 合肥国轩高科动力能源股份公司 | Preparation method of aluminum-oxide-coated nano lithium titanate composite material |
| CN102437369B (en) * | 2011-12-20 | 2014-07-02 | 中国东方电气集团有限公司 | Lithium ion battery |
-
2012
- 2012-12-20 CN CN201210557799.5A patent/CN103035901B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103035901A (en) | 2013-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103035901B (en) | Nanometer oxide coated lithium titanate negative electrode material of lithium battery, and preparation method for negative electrode material | |
| CN109167020B (en) | Porous lithium ion pole piece with high energy density, preparation method thereof and lithium ion battery | |
| CN106299314B (en) | A kind of lithium ion battery negative material and preparation method thereof, lithium ion battery | |
| CN102299311B (en) | Cathode active material and preparation method thereof and lithium ion secondary battery prepared by cathode active material | |
| WO2012146046A1 (en) | Polyimide capacitance battery and manufacturing method thereof | |
| CN104916825A (en) | Preparation method of lithium battery high-voltage modified cathode material | |
| CN103928668B (en) | Lithium ion battery and preparation method of anode material thereof | |
| CN105226274A (en) | A kind of preparation method of LiFePO4/graphene composite material of graphene uniform dispersion | |
| CN112614703B (en) | Negative electrode material of ionic capacitor and preparation method and application thereof | |
| CN103000378A (en) | Preparation method of cathode active material and preparation method of capacitor | |
| CN103000383A (en) | Super capacitance battery and preparation method thereof | |
| CN105390295A (en) | Lithium-ion capacitor, and negative material and negative electrode plate thereof | |
| CN102544507B (en) | Lithium ion power battery positive plate and lithium ion power battery | |
| CN103000385A (en) | Super hybrid capacitance battery and preparation method thereof | |
| CN117174873A (en) | Preparation method of positive electrode material, positive electrode plate, sodium ion battery and power utilization device | |
| CN109461917B (en) | Preparation method of lanthanum zirconate in-situ coated high-nickel ternary cathode material | |
| JP2022530294A (en) | Electrolyte and electrochemical equipment | |
| JP2022553518A (en) | Secondary battery and device provided with the secondary battery | |
| CN106803575A (en) | A kind of anode material for lithium-ion batteries and its preparation method and application | |
| CN111696792B (en) | Organic nanometer negative electrode based on insertion layer type pseudo-capacitor and preparation method and application thereof | |
| CN104409704A (en) | Nano porous oxide electrode material for lithium ion battery | |
| CN101527370A (en) | Power lithium ion battery | |
| CN114864916A (en) | Niobium pentoxide coated graphite composite negative electrode material and preparation method thereof | |
| WO2023087209A1 (en) | Electrochemical device and electronic device | |
| WO2021127999A1 (en) | Secondary battery and apparatus containing secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180425 Address after: 610000 18 West core road, hi-tech West District, Chengdu, Sichuan Patentee after: Dongfang Electric Co., Ltd. Address before: 610036 Shu Han Road, Jinniu District, Chengdu, Sichuan Province, No. 333 Patentee before: Dongfang Electric Corporation |
|
| TR01 | Transfer of patent right |