CN102456868B - Lithium titanate composite material and preparation method thereof and lithium ion battery - Google Patents
Lithium titanate composite material and preparation method thereof and lithium ion battery Download PDFInfo
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- CN102456868B CN102456868B CN201010529980.6A CN201010529980A CN102456868B CN 102456868 B CN102456868 B CN 102456868B CN 201010529980 A CN201010529980 A CN 201010529980A CN 102456868 B CN102456868 B CN 102456868B
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Abstract
The invention relates to a lithium titanate composite material which comprises lithium titanate particles and an aluminum phosphate layer cladded on the surface of the lithium titanate particles. The invention also relates to a preparation method of a lithium nickelate composite material, and a lithium ion battery.
Description
Technical field
The present invention relates to a kind of lithium titanate composite material and preparation method thereof, and lithium ion battery.
Background technology
To the particle surface of active substance of lithium ion battery anode, adopting other material to form coated, is in prior art, positive active material to be carried out the common method of modification.For example, at the coated one deck carbon of the particle surface of LiFePO4, can effectively solve the problem that LiFePO4 conductivity is lower, make the LiFePO4 that is coated with carbon-coating there is good conductivity.In addition, prior art shows, and the thermal stability that can improve lithium ion cell positive at cobalt acid lithium or the coated aluminum phosphate of other positive active material particle surface (refers to document " Correlation between AlPO
4nanoparticle coating thickness on LiCoO
2cathodeand thermal stablility " J.Cho, Electrochimica Acta 48 (2003) 2807-2811 and the patent No. are 7,326,498 United States Patent (USP)).
In prior art, by the method for aluminum phosphate clad anode active material, be first to prepare aluminum phosphate particle to be scattered in and in water, to form dispersion liquid, and positive active material particle is added in the dispersion liquid of this aluminum phosphate particle preparing, effect by absorption makes aluminum phosphate particle be adsorbed on positive active material large particle surface, again by the water evaporate to dryness in dispersion liquid, and heat treatment at 700 ℃, form the positive active material that surface has aluminum phosphate particle.
Yet, because aluminum phosphate is water insoluble, when disperseing in water, aluminum phosphate particle may form reunion, and when a large amount of positive active materials are added in aluminum phosphate dispersion liquid, the positive active material first adding adsorbs a large amount of aluminum phosphate particles, after the positive active material particle that adds may adsorb less than enough aluminum phosphate particles.Refer to Fig. 8, even if can be good at being coated, said method determines that this product 20 is aluminum phosphate from microcosmic and is distributed in positive active material bulky grain 24 surfaces with the form of granule 22, not the even aluminum phosphate material layer of one deck.Therefore, the aluminum phosphate coating layer forming on positive active material surface by said method is even not, cannot guarantee that each positive active material surface all can be coated one deck aluminum phosphate uniformly, thereby the cycle performance of lithium ion battery that makes to apply this positive active material is bad, make the method be difficult to heavy industrialization application.
Summary of the invention
In view of this, necessaryly provide a kind of and can form at lithium titanate particle surface the method for even aluminum phosphate coating layer, and there is the lithium titanate composite material of this aluminum phosphate coating layer, and the lithium ion battery of applying this lithium titanate composite material.
A lithium titanate composite material, the phosphoric acid aluminium lamination that it comprises lithium titanate particle and is coated on this lithium titanate particle surface.
A preparation method for lithium titanate composite material, it comprises: aluminum nitrate solution is provided; Lithium titanate particle to be covered is added in this aluminum nitrate solution, form mixture; Add this mixture to react phosphate solution, at this lithium titanate particle surface, form phosphoric acid aluminium lamination; And this surface of heat treatment has the lithium titanate particle of phosphoric acid aluminium lamination.
A lithium ion battery, it comprises positive pole and negative pole, this negative pole comprises described lithium titanate composite material.
Compared to prior art, the present invention has avoided, because the absorption of solid mixing generation is inhomogeneous, causing aluminum phosphate to be coated uneven phenomenon, is applicable to heavy industrialization application.In addition, the present invention can be at the even and continuous phosphoric acid aluminium lamination of electrode active material particles Surface Creation a layer thickness, but not by aluminum phosphate particle packing on electrode active material particles surface, therefore there is better chemical property.
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiment of the present invention aluminum phosphate jacketed electrode active material.
Fig. 2 is the stereoscan photograph of the coated cobalt acid of embodiment of the present invention aluminum phosphate lithium.
Fig. 3 is the transmission electron microscope photo of the coated cobalt acid of embodiment of the present invention aluminum phosphate lithium.
Fig. 4 is the cycle performance test curve of the coated cobalt acid lithium of embodiment of the present invention aluminum phosphate.
Fig. 5 is the stereoscan photograph that the aluminum phosphate of contrast experiment's low power amplification is coated cobalt acid lithium.
Fig. 6 is the stereoscan photograph that the aluminum phosphate of contrast experiment's magnification at high multiple is coated cobalt acid lithium.
Fig. 7 is the cycle performance test curve of the coated electrode active material of contrast experiment's aluminum phosphate.
Fig. 8 is the structural representation of the aluminum phosphate jacketed electrode active material of prior art.
Main element symbol description
Anode composite material particle 10
Electrode active material particles 12
Phosphoric acid aluminium lamination 14
Granule 22
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments to lithium titanate composite material provided by the invention and preparation method thereof, and lithium ion battery is described in further detail.
Refer to Fig. 1, the embodiment of the present invention provides a kind of electrode active material composite material 10 for lithium ion cell positive or negative pole, the phosphoric acid aluminium lamination 14 that this electrode active material composite material 10 comprises electrode active material particles 12 and is coated on this electrode active material particles surface.This electrode active material particles 12 can be positive active material particle or anode active material particles.
The mass percent of this phosphoric acid aluminium lamination 14 in this electrode active material composite material 10 is 0.1% to 3%.The thickness of this phosphoric acid aluminium lamination 14 is preferably 5 nanometer to 20 nanometers.This phosphoric acid aluminium lamination 14 is created on this electrode active material particles 12 surfaces for original position.This phosphoric acid aluminium lamination 14 is even thickness and continuous aluminum phosphate material layer.The all surface of this electrode active material particles 12 is all covered by this continuous phosphoric acid aluminium lamination 14.Further, in the interface of 12 of this phosphoric acid aluminium lamination 14 and this electrode active material particles, may form interfacial diffusion, metallic atom is diffused in this phosphoric acid aluminium lamination 14.
When this electrode active material particles 12 is positive active material particle, the material of this electrode active material particles 12 can be one or more in cobalt acid lithium, spinel lithium manganate, layered lithium manganate, LiFePO4, lithium nickelate, Li, Ni, Mn oxide and lithium nickel cobalt manganese oxide.For example, the material of this electrode active material particles 12 can be by chemical formula Li
xco
(1-y)m
yo
2represent 0.1≤x≤1.1 wherein, 0≤y < 1.When this electrode active material particles 12 is anode active material particles, the material of this electrode active material particles 12 can be the lithium titanate of non-doping or the lithium titanate of doping.The lithium titanate of this non-doping or the lithium titanate of doping have spinel structure.Particularly, the chemical formula of the lithium titanate of this non-doping is Li
4ti
5o
12, the chemical formula of the lithium titanate of this doping can be by Li
(4-a)maTi
5o
12or Li
4m
bti
(5-b)o
12represent wherein 0 < a≤0.33, and 0 < b≤0.5.
Described M is selected from one or more in alkali metal, alkali earth metal, 13 family element, 14 family element, transition element and rare earth element, and preferably, M is selected from least one in Mn, Cr, V, Ni, Co, Al, Fe, Ga and Mg.
The particle diameter of described electrode active material particles 12 is preferably 100 nanometers to 100 micron, more preferably 1 micron to 20 microns.
It is a kind of by the electrode active material particles of aluminum phosphate coated lithium ion battery 12 that the embodiment of the present invention provides, and forms the method for described electrode active material composite material 10, and it comprises the following steps:
Step 2, adds electrode active material particles to be covered in this aluminum nitrate solution, forms a mixture;
Step 3, adds this mixture to react phosphate solution, makes this electrode active material particles surface form phosphoric acid aluminium lamination; And
Step 4, this surface of heat treatment has the electrode active material particles of phosphoric acid aluminium lamination, obtains electrode active material composite material.
This aluminum nitrate solution comprises liquid phase solvent and is dissolved in the aluminum nitrate of this solvent (Al (NO
3)
3).Being appreciated that this solvent is chosen as can make aluminum nitrate dissociate to form Al
3+solvent.Therefore this solvent is not limited to water, can also be volatile organic solvent, and preferably, this solvent is one or several mixing in ethanol, acetone, dichloroethanes and chloroform.With respect to adopting water as solvent, using organic solvent if ethanol is as solvent, can avoid electrode active material particles to react with water electrode active material performance is reduced.
In above-mentioned steps two, this electrode active material particles is lithium titanate particle, and this electrode active material particles is insoluble to this aluminum nitrate solution, and both are that solid-liquid mixes, and object is that the surface uniform in this electrode active material particles adheres to one deck Al
3+.Due to Al
3+with ionic species, exist, can be attached to uniformly electrode active material particles surface, this electrode active material particles is formed to the coated of atom level.Further, can control the addition of this electrode active material particles, controlled being made as of ratio of this electrode active material particles and aluminum nitrate solution makes this aluminum nitrate solution can cover this electrode active material particles surface, makes the mixture obtaining be muddy.The object that forms muddy mixture is mainly just enough on electrode active material particles surface, to form one deck aluminum phosphate coating layer in order to control the addition of aluminum nitrate solution.Particularly, the volume of this aluminum nitrate solution and the volume ratio of this electrode active material particles are about 1: 10 to 1: 40.The particle diameter of this electrode active material particles is preferably and is less than 20 microns.The aluminum phosphate coating layer that the addition of this aluminum nitrate solution can form by needs accounts for the mass percent of electrode active material composite material granular and is determined, preferably, the mass percent of this aluminum phosphate coating layer in this electrode active material composite material is 0.1% to 3%.
In above-mentioned steps three, this phosphate solution comprises that water is as solvent, and the soluble phosphate that is dissolved in this solvent, as phosphoric acid ammonia salt.This phosphoric acid ammonia salt comprises ammonium dihydrogen phosphate (NH
4h
2pO
4), diammonium hydrogen phosphate ((NH
4)
2hPO
4) and triammonium phosphate ((NH
4)
3pO
4) in one or more mixing.In this phosphate solution, contain phosphate anion.This phosphate anion can be positive phosphorus acid ion (PO
4 3-), dihydrogen phosphate ions (H
2pO
4 -) and phosphoric acid one hydrogen radical ion (HPO
4 2-) in one or more mixing.When this phosphate solution is added to described muddy mixture, this phosphate anion and the Al that is attached to electrode active material particles surface
3+reaction, thus at electrode active material particles surface in situ, form the uniform aluminum phosphate precipitation of one deck.Preferably, this phosphate solution can dropwise add this muddy mixture, and is stirred, thereby makes this phosphate anion and this Al
3+can be in the reaction of this electrode active material particles surface uniform.With aluminum nitrate solution similarly, the aluminum phosphate coating layer that the addition of this phosphate solution can form by needs accounts for the mass percent of electrode active material composite material granular and is determined.Preferably, the phosphate anion in this phosphate and the aluminum ions mol ratio in this aluminum nitrate are about 1: 1.
In above-mentioned steps four, this heat treated object is to make the better combination in interface of this aluminum phosphate and electrode active material particles, forms composite material, and removes the ammonium nitrate of residual solvent and reaction generation.By this heat treatment, in the interface of aluminum phosphate and electrode active material particles, may form interfacial diffusion, make the metallic atom in electrode active material particles, as Ti or Li, diffuse in this phosphoric acid aluminium lamination.This heat treatment temperature can be 400 ℃ to 800 ℃.This heat treated time is preferably 0.5 to 2 hour.
Because this method first joins electrode active material particles in aluminum nitrate solution, in this aluminum nitrate solution, add again and can react with aluminium ion the phosphate solution that generates aluminum phosphate, thereby generate the continuous phosphoric acid aluminium lamination of one deck at electrode active material particles surface in situ.Because the aluminum nitrate solution of liquid phase and the electrode active material particles of solid phase are mixed, can first make aluminium ion be coated on uniformly this electrode active material particles surface, therefore the aluminum phosphate precipitation, being generated by aluminium ion after reaction in-situ also can be more even and continuous be coated on the whole surface of this electrode active material particles.With first synthetic aluminum phosphate particle, the mode that makes aluminum phosphate particle be adsorbed onto electrode active material particles surface by suction-operated is again compared, this method has been avoided because the absorption of solid mixing generation is inhomogeneous, cause aluminum phosphate to be coated inhomogeneous, discontinuous or coated incomplete phenomenon, be applicable to heavy industrialization application.In addition, this method can be at the even thickness of electrode active material particles Surface Creation intact and continuous phosphoric acid aluminium lamination, but not by aluminum phosphate particle packing on electrode active material particles surface.This phosphoric acid aluminium lamination can pass through ion in the electron transfer between isolated electrolyte and active material, thereby when completing the embedding of lithium ion and deviating from, avoid electrolyte to decompose under high voltage or higher temperature, therefore make this electrode active material can under high voltage or higher temperature, there is better battery performance and Capacitance reserve performance.
The embodiment of the present invention further provides a kind of lithium ion battery, and this lithium ion battery comprises positive pole, negative pole and the nonaqueous electrolyte between positive pole and negative pole.This positive pole comprises plus plate current-collecting body and is arranged on the positive electrode material layer of this anode collection surface, and this negative pole comprises negative current collector and is arranged on the negative electrode material layer of this negative pole currect collecting surface.
This positive electrode material layer can comprise mixing of described positive electrode active material composite material and conductive agent and binding agent, and this positive electrode active material composite material comprises positive active material particle and is coated on the described phosphoric acid aluminium lamination of this positive active material particle surface.The material of this positive active material particle can be one or more in cobalt acid lithium, spinel lithium manganate, layered lithium manganate, LiFePO4, lithium nickelate, Li, Ni, Mn oxide and lithium nickel cobalt manganese oxide.This negative electrode material layer can comprise mixing of described negative electrode active material composite material and conductive agent and binding agent, and this negative electrode active material composite material comprises anode active material particles and is coated on the described phosphoric acid aluminium lamination on this anode active material particles surface.The material of this anode active material particles can be lithium titanate.This conductive agent can be one or more in acetylene black, carbon fiber, carbon nano-tube and graphite.This binding agent can be one or more in Kynoar (PVDF), polytetrafluoroethylene (PTFE) and butadiene-styrene rubber (SBR).This nonaqueous electrolyte can be nonaqueous electrolytic solution or solid electrolyte film.Adopt the lithium ion battery of this nonaqueous electrolytic solution further to comprise and be arranged on barrier film between this positive electrode material layer and negative electrode material layer.Adopt the lithium ion battery of this solid electrolyte film that this solid electrolyte film is arranged between this positive electrode material layer and negative electrode material layer.This nonaqueous electrolytic solution comprises solvent and is dissolved in the solute of solvent, this solvent can be enumerated as one or more in cyclic carbonate, linear carbonate, ring-type ethers, chain ethers, nitrile and amide-type, as ethylene carbonate, propene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, oxolane, 1,2-dimethoxy-ethane, acetonitrile and dimethyl formamide.This solute can be enumerated as LiPF
6, LiBF
4, LiCF
3sO
3, LiAsF
6, LiClO
4and one or more in LiBOB.The material of this solid electrolyte film can be enumerated as LiI, LiN
3or the mixing of the solute of the polymeric matrix such as polyoxyethylene or polyacrylonitrile and above-mentioned nonaqueous electrolytic solution.
The embodiment of the present invention specifically adopts said method to prepare described electrode active material composite material granular by aluminum phosphate jacketed electrode active material particle, and this electrode active material composite material granular is applied to carry out in lithium ion battery performance test.
In the present embodiment, this electrode active material particles is positive active material cobalt acid lithium particle, and chemical formula is LiCoO
2.This aluminum phosphate-cobalt acid lithium composite material comprises cobalt acid lithium particle and is coated on the phosphoric acid aluminium lamination of this cobalt acid lithium particle surface.
In the preparation of this aluminum phosphate-cobalt acid lithium composite material, this aluminum nitrate solution is the solution that aluminum nitrate forms in ethanol.The volume of this aluminum nitrate solution is 30 milliliters, and molar concentration is 0.16 mol/L.The addition of this cobalt acid lithium particle is 100g.This phosphate solution is (NH
4)
2hPO
4the aqueous solution.Should (NH
4)
2hPO
4with Al (NO
3)
3mol ratio be 1: 1.In heat treatment temperature, be respectively 400 ℃, 500 ℃ and 600 ℃, phosphoric acid aluminium lamination accounts for and under the condition that the mass percent of gross mass is 1%, prepares 3 kinds of aluminum phosphates-cobalt acid lithium composite material particulate samples.In addition, in heat treatment temperature, be 600 ℃, phosphoric acid aluminium lamination accounts for and under the condition that the mass percent of gross mass is 1.5%, prepares a kind of aluminum phosphate-cobalt acid lithium composite material sample.Refer to Fig. 2 and Fig. 3, in the sample obtaining, phosphoric acid aluminium lamination is coated on this cobalt acid lithium particle surface uniformly, by high magnification transmission electron microscope observing, can clearly see that this aluminum phosphate is that form with the material layer of even thickness covers this cobalt acid lithium particle surface surface.Respectively using these 4 kinds of samples as positive electrode active materials, mix with a certain proportion of conductive agent and binding agent and be coated on anode collection surface and make positive pole, using metal lithium sheet as negative pole, positive pole and negative pole are infiltrated and are assembled into lithium ion battery by barrier film interval and with electrolyte, carry out charge-discharge performance test.
Be coated with the electrode active material particles of aluminum phosphate, owing to playing the aluminum phosphate of coating function and improved the surface texture of electrode active material particles, to lithium ion, provide the de-platform of owing, play the effect on barrier layer simultaneously, effectively suppressing tetravalence cobalt ions reacts with electrolyte, stablize cobalt acid lithium structure, improved electrochemistry cycle performance.Refer to Fig. 4, above-mentioned 4 kinds of samples are carried out to constant current charge-discharge loop test under 0.5C electric current, the cut-ff voltage of this charging is 4.5V, and the cut-ff voltage of electric discharge is 2.7V.From figure, can find, the sample that adopts the inventive method to prepare, because aluminum phosphate can be coated cobalt acid alumina particles uniformly, under high voltage, charging still can have higher capacity and stable capability retention, capability retention after 50 circulations is all more than 90%, and specific capacity is 160mAh/g to 175mAh/g.And along with the raising of heat treatment temperature, the capacity of battery increases to some extent.The change of this aluminum phosphate percentage composition is little on the impact of battery capacity.
Embodiment 2
In the present embodiment, this electrode active material particles is negative electrode active material lithium titanate particle, and chemical formula is Li
4ti
5o
12.This aluminum phosphate-lithium titanate composite material comprises lithium titanate particle and is coated on the phosphoric acid aluminium lamination of this lithium titanate particle surface.
The preparation method of this aluminum phosphate-lithium nickelate composite material is identical with the preparation method of the aluminum phosphate of above-described embodiment 1-cobalt acid lithium composite material particle, heat treatment temperature is chosen as 600 ℃, the mass percent that phosphoric acid aluminium lamination accounts for gross mass is 1.5%, and difference is only lithium titanate at the material of electrode active material particles.Using this aluminum phosphate-lithium titanate composite material as negative active core-shell material, mix with a certain proportion of conductive agent and binding agent and be coated on negative pole currect collecting surface and make negative pole, using metal lithium sheet as positive pole, positive pole and negative pole are infiltrated and are assembled into lithium ion battery by barrier film interval and with electrolyte, carry out charge-discharge performance test.Due to aluminum phosphate coating spinelle lithium titanate particle uniformly, in wide temperature range, (as 15 ℃ to 60 ℃) charging still can have higher capacity and stable capability retention.This lithium ion battery is carried out under 0.1C electric current at 55 ℃ to constant current charge-discharge loop test, voltage range is 0.8V to 3V, and after 50 circulations, the capability retention of battery is all more than 85%, and specific capacity is about 160mAh/g.
For contrasting with the anode composite material particle of embodiment 1 preparation, with the method for prior art, prepare comparative sample, concrete steps are: by (NH
4)
2hPO
4the aqueous solution mixes with aluminum nitrate aqueous solution, generates aluminum phosphate particle in water, forms dispersion liquid; Cobalt acid lithium particle is dropped in this dispersion liquid, by the effect of adsorbing, make aluminum phosphate particle be adsorbed on cobalt acid lithium particle surface; And at 600 ℃, this adsorption of heat treatment has the cobalt acid lithium particle of aluminum phosphate particle, obtains described comparative sample.Refer to Fig. 5 and Fig. 6, in the comparative sample of preparing by art methods, aluminum phosphate is that the form of particle is gathered in this cobalt acid lithium particle surface, and aluminum phosphate particle reunites, and makes to be coated inhomogeneous.
Using this comparative sample as positive electrode active materials, assembled battery under the condition identical with embodiment 1, carries out charge-discharge performance test.Also using the cobalt acid lithium particle that is not coated any material as positive electrode active materials, under the condition identical with embodiment 1, be assembled into lithium ion battery in addition, carry out charge-discharge performance test.Above-described embodiment 1 is only positive electrode active materials with this contrast experiment's difference, and other battery condition and test condition are all identical.
Refer to Fig. 7, the circulation volume of this comparative sample and not coated cobalt acid lithium particulate samples sharply declines, capability retention after 50 circulations is all less than 85%, this is mainly owing to using the method for prior art easily to make cobalt acid lithium particle coated inhomogeneous or not coated, while making under high pressure to charge, cobalt acid lithium and electrolyte react and make the volume lowering of battery.
Contrast experiment 2
Adopt the method identical with contrast test 1 to be coated lithium titanate particle, preparation comparative sample, under the condition identical with above-described embodiment 2, be assembled into lithium ion battery, owing to using the method for prior art easily to make negative active core-shell material coated inhomogeneous, this lithium ion battery is carried out under 0.1C electric current at 55 ℃ to constant current charge-discharge loop test, voltage range is 0.8V to 3V, and after 50 circulations, the capability retention of battery is less than 85%.
In addition, those skilled in the art also can do other and change in spirit of the present invention, and certainly, the variation that these are done according to spirit of the present invention, within all should being included in the present invention's scope required for protection.
Claims (15)
1. a preparation method for lithium titanate composite material, it comprises:
Aluminum nitrate solution is provided;
Lithium titanate particle to be covered is added in this aluminum nitrate solution, and the volume ratio of the volume of this aluminum nitrate solution and this lithium titanate particle is 1:10 to 1:40, forms muddy mixture;
Add this mixture to react phosphate solution, at this lithium titanate particle surface, form phosphoric acid aluminium lamination; And
This surface of heat treatment has the lithium titanate particle of phosphoric acid aluminium lamination.
2. the preparation method of lithium titanate composite material as claimed in claim 1, is characterized in that, this aluminum nitrate solution comprises solvent and be dissolved in the aluminum nitrate of this solvent, and this solvent is ethanol.
3. the preparation method of lithium titanate composite material as claimed in claim 1, it is characterized in that, this phosphate solution comprises water and is dissolved in the phosphoric acid ammonia salt of water, and this phosphoric acid ammonia salt comprises one or more the mixing in ammonium dihydrogen phosphate, diammonium hydrogen phosphate and triammonium phosphate.
4. the preparation method of lithium titanate composite material as claimed in claim 1, is characterized in that, this heat treatment temperature is 400 ℃ to 600 ℃.
5. a lithium titanate composite material, prepared by the preparation method by lithium titanate composite material as claimed in claim 1, this lithium titanate composite material comprises lithium titanate particle, it is characterized in that, further comprise the phosphoric acid aluminium lamination that is coated on this lithium titanate particle surface, this aluminum phosphate layer thickness is even and continuous.
6. lithium titanate composite material as claimed in claim 5, is characterized in that, the mass percent of described phosphoric acid aluminium lamination in this lithium titanate composite material is 0.1% to 3%.
7. lithium titanate composite material as claimed in claim 5, is characterized in that, the mass percent of described phosphoric acid aluminium lamination in this lithium titanate composite material is 1%.
8. lithium titanate composite material as claimed in claim 5, is characterized in that, the thickness of described phosphoric acid aluminium lamination is 5 nanometer to 20 nanometers.
9. lithium titanate composite material as claimed in claim 5, is characterized in that, described phosphoric acid aluminium lamination is that original position is created on this lithium titanate particle surface.
10. lithium titanate composite material as claimed in claim 5, is characterized in that, the material of described lithium titanate particle is the lithium titanate of doping or non-doping, and the chemical formula of the lithium titanate of this non-doping is Li
4ti
5o
12, the chemical formula of the lithium titanate of this doping is by Li
(4-a)m
ati
5o
12or Li
4m
bti
(5-b)o
12represent, 0<a≤0.33 wherein, 0<b≤0.5, and M is selected from one or more in alkali metal, alkali earth metal, 13 family element, 14 family element, transition element and rare earth element.
11. lithium titanate composite materials as claimed in claim 5, is characterized in that, the particle diameter of described lithium titanate particle is 100 nanometers to 100 micron.
12. lithium titanate composite materials as claimed in claim 11, is characterized in that, the particle diameter of described lithium titanate particle is 1 micron to 20 microns.
13. 1 kinds of lithium ion batteries, it comprises positive pole and negative pole, it is characterized in that, this negative pole comprises lithium titanate composite material as claimed in claim 5.
14. lithium ion batteries as claimed in claim 13, is characterized in that, this positive pole comprises positive active material particle and is coated on the phosphoric acid aluminium lamination of this positive active material particle surface.
15. lithium ion batteries as claimed in claim 14, it is characterized in that, the material of this positive active material particle is one or more in cobalt acid lithium, spinel lithium manganate, layered lithium manganate, LiFePO4, lithium nickelate, Li, Ni, Mn oxide and lithium nickel cobalt manganese oxide.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010529980.6A CN102456868B (en) | 2010-11-03 | 2010-11-03 | Lithium titanate composite material and preparation method thereof and lithium ion battery |
| US13/092,135 US8568620B2 (en) | 2010-08-02 | 2011-04-21 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/107,006 US20120028120A1 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/106,996 US9054379B2 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/106,994 US9219276B2 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/107,003 US9203087B2 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/106,999 US8349494B2 (en) | 2010-08-02 | 2011-05-13 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| US13/108,101 US8277979B2 (en) | 2010-08-02 | 2011-05-16 | Electrode composite material, method for making the same, and lithium ion battery using the same |
| JP2011146856A JP5373857B2 (en) | 2010-11-03 | 2011-06-30 | ELECTRODE COMPOSITE MATERIAL, ITS MANUFACTURING METHOD, AND LITHIUM ION BATTERY USING THE SAME |
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| CN105633355B (en) * | 2014-11-03 | 2017-12-05 | 龙能科技（苏州）有限公司 | Lithium titanate composite material and preparation method thereof, electrochemical cell |
| CN104852035B (en) * | 2015-04-28 | 2017-07-07 | 湖南瑞翔新材料股份有限公司 | The preparation method of the lithium titanate of alumina-coated |
| CN109713283A (en) * | 2018-12-29 | 2019-05-03 | 江苏特丰新材料科技有限公司 | The lithium titanate composite material and preparation method thereof of phosphorus aluminium cladding |
| CN111463411A (en) * | 2019-01-18 | 2020-07-28 | 天津国安盟固利新材料科技股份有限公司 | High-nickel ternary cathode material with single crystal morphology and preparation method thereof |
| JP7225282B2 (en) * | 2021-02-08 | 2023-02-20 | プライムプラネットエナジー＆ソリューションズ株式会社 | Positive electrode active material and lithium ion secondary battery comprising the positive electrode active material |
| CN115611306B (en) * | 2022-10-31 | 2023-12-26 | 上海意定新材料科技有限公司 | Negative electrode material of lithium ion power battery and preparation method thereof |
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| CN101764207A (en) * | 2009-09-25 | 2010-06-30 | 合肥工业大学 | Lithium titanate for lithium ion battery negative electrode material and preparation method thereof |
| 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 |
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| KR100508941B1 (en) * | 2003-11-29 | 2005-08-17 | 삼성에스디아이 주식회사 | Method of preparing positive active material for rechargeable lithium battery and positive active material for rechargeable lithium battery fabricated using same |
| CN1328805C (en) * | 2004-04-05 | 2007-07-25 | 中国科学院物理研究所 | Negative electrode active material and use of secondary lithium battery |
| JP4679112B2 (en) * | 2004-10-29 | 2011-04-27 | 三洋電機株式会社 | Non-aqueous electrolyte secondary battery and manufacturing method thereof |
| US8367253B2 (en) * | 2006-02-02 | 2013-02-05 | U Chicago Argonne Llc | Lithium-ion batteries with intrinsic pulse overcharge protection |
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