CN1797822A - Method for modified cladding composite, anode material LiCoO* of lithium ion battery, and batteries - Google Patents
Method for modified cladding composite, anode material LiCoO* of lithium ion battery, and batteries Download PDFInfo
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- CN1797822A CN1797822A CNA2004100816641A CN200410081664A CN1797822A CN 1797822 A CN1797822 A CN 1797822A CN A2004100816641 A CNA2004100816641 A CN A2004100816641A CN 200410081664 A CN200410081664 A CN 200410081664A CN 1797822 A CN1797822 A CN 1797822A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The composite material is LiCoO2 powdered material with surface being coated by conductive glass layer. The method includes steps: (1) mixing the said powdered material with solution capable of generating oxide or conductive glass layer for coating surface of the powdered material; (2) adding solution of organic high molecular material to admixture in step (1) or after step (1); (3) after procedures of de-watering, firing and calcining the admixture so as to obtain coated LiCoO2. The battery includes positive pole made from the disclosed composite material. The organic high molecular material not only disperses material to be coated, but also plays function of binder so that oxide or conductive glass layer can be dispersed in solution evenly and can coat on surface of LiCoO2 powdered material evenly. The invention raises thermal stability and reserves good process performance.
Description
[technical field]
The present invention relates to materials chemistry field and high-energy battery technology, be specifically related to a kind of compound, anode material for lithium-ion batteries LiCoO
2Method for modified cladding and the battery that adopts this method to make.
[background technology]
Make negative pole with the graphite-like material with carbon element that can embed and deviate from lithium ion, transition oxide is done anodal, and the chargeable lithium ion battery that adopts the non-aqueous organic solvent lithium salt solution to make electrolyte is a digital Age mobile phone and portable type electronic product, as the main power supply of notebook computer, PDA, camcorder, digital camera and electric tool etc., have that energy density is big, operating voltage is high, have extended cycle life, characteristics such as memory-less effect and high environmental protection.
At present, lithium ion battery has developed into the industry of annual sales amount nearly 3,000,000,000 more than.Although industry has had so big scale, still there are many improved problems of demanding urgently with regard to its product, as battery safety etc.
As everyone knows, the commodity lithium ion battery is used cobalt acid lithium LiCoO always
2Make the positive electrode of battery.LiMn
2O
4And LiNi
1-xCo
xO
2Still have major defect, still can not replace LiCoO
2LiCoO
2Though the processing behavior is good, specific capacity is big, cycle performance is good, be the very good positive electrode of combination property, 4 valency cobalt (CoO under Charging state
2) have very strong oxidizability, and its oxidizing force increases and strengthens with taking off the lithium degree.So many and LiCoO
2Have during relevant accident report (referring to Laptop Batteries Are Linked to Fire Risk, New York Times, March 15,2001; US Consumer ProductSafety Commission).Its main cause is LiCoO when overcharging
2Anodal together with the fierce exothermic reaction of electrolyte generation.
In order to eliminate this danger, people have carried out various effort, and propose with various oxides (as Al
2O
3, ZrO
2, TiO
2, SnO
2, MgO) coating coats LiCoO
2The cathode material particle surface is to improve LiCoO
2The method of thermal stability (seeing Ho-Jin Kweon et al, Journal of Power Source 126 (2004) 156-162).Cho etc. propose with the salt nano coating (as AlPO
4) coat (J.Cho et al Angew. (Chem.Int.Ed.42 (2003) 1618)).Yet these oxides and salt mostly are dielectric film greatly, coat the specific capacity that often causes coating the back positive electrode with them and descend.In addition, even more serious is that very big change has taken place for the granular size and the surface thereof that coat the back active material, and it is bad that slurry processing behavior becomes, and is difficult to the processing and manufacturing electrode.So it is very necessary developing the new anodal thermal stability of method for coating improvement.
[summary of the invention]
The technical problem to be solved in the present invention provides a kind of at raising LiCoO
2Still make its method for modified cladding in the time of the particle thermal stability with well processed behavior, and a kind of lithium ion battery that is just having good thermal stability.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of anode material for lithium-ion batteries LiCoO
2Method for modified cladding, comprise the steps:
1) with LiCoO
2Powder mixes stirring with the solution that can generate oxide or conductive glass surface coating layer;
2) when carrying out step 1) or after carrying out step 1), also add high-molecular organic material solution;
3) said mixture is obtained the surface through coating the LiCoO that handles after dewatering, toast, calcining
2
And a kind of lithium ion battery comprises positive plate, and described positive plate is by containing the surface through coating the LiCoO that handles
2Anode sizing agent make the LiCoO of described surface through coat handling
2Make through above-mentioned steps.
But described high-molecular organic material solution applies one or more the aqueous solution in occasion preferably polyethylene alcohol (PVA), polyethylene glycol oxide (PEO), polyacrylamide, polytetrafluoroethylene (PTFE), polypropylene pyrrolidones, butadiene-styrene rubber (SBR), the soluble starch at the aqueous solution; In oil phase dip-coating occasion, the preferably bipolymer (VDF-HFP) of polyvinylidene fluoride resin (PVDF), vinylidene and hexafluoropropylene, one or more organic solvents in the low molecular weight polyacrylate.
The quality percentage composition of the aqueous solution of described high-molecular organic material preferred 0.1% to 5%.
Described oxide surface coating layer can be MgO, B
2O
3, Al
2O
3, Fe
2O
3, SiO
2, SnO
2, TiO
2, ZrO
2In at least a.
Described conductive glass surface coating layer can be
1)XLi
2O·(1-X)B
2O
3；
2)XLi
2O·YAl
2O
3·(1-X-Y)B
2O
3；
3)XLi
2O·(1-X)SiO
2；
4)XLi
2O·YAl
2O
3·(1-X-Y)SiO
2；
5)XLiF·(1-X)LiPO
3；
6)XLiF·(1-X)Al(PO
3)
3；
7)XLiF·YKF·(1-X-Y)Al(PO
3)
3；
8)XLiMn
2O
4·(1-X)B
2O
3
9)XLi
2O·YMnO
2-x·(1-X-Y)B
2O
3；
10)(100-X)(YLi
2S·ZB
2S
3)·XLi
xMO
y；
11)(100-X)(YLi
2S·ZGeS
2)·XLi
xMO
y；
12)(100-X)(YLi
2S·ZP
2O
5)·XLi
xMO
y；
13)(100-X)(YLi
2S·ZSiS
2)·XLi
xMO
y；
14)XAgI·YAg
2O·(1-X-Y)M
xO
y；
In any one, wherein: 1)～9) in 0.1≤X≤0.9,0≤Y≤(1-X); 10) 0≤X～13)≤0.4,0.1＜Y＜0.9,0＜Z＜(1-Y), Li
xMO
y=Li
4SiO
4, Li
3PO
4, Li
4GeO
4, Li
3BO
3, Li
3AlO
3, Li
3GaO
3, Li
3InO
314) 0.1≤X in≤0.9, M
xO
y=MoO
3, SeO
3, WO
3, P
2O
5, GeO
2
Preferred 40 ℃ to 100 ℃ of heating-up temperature in the described removal process.
Preferred 50 ℃ to 120 ℃ of baking temperature in the described bake process.
Preferred 220 ℃ to 1000 ℃ of calcining heat in the described calcination process, calcination time are 4h to 8h.Single phase calcining at constant temperature method is calcined or adopted to the method that described calcination process can adopt the multistage progressively to heat up.
Adopt technique scheme, beneficial technical effects of the present invention is: 1) at LiCoO
2Add high-molecular organic material in the coating decoration process of positive electrode, not only can disperse encapsulated material, also play the effect of binder, by preparation method provided by the invention, the oxide that is used for coating, electro-conductive glass particle or elements corresponding raw material can be scattered in solution equably and be coated on LiCoO equably
2On the positive electrode particle surface, make and improving LiCoO
2Still keep its good processing behavior in the time of the particle thermal stability; 2) use electro-conductive glass as coating film, overcome the shortcoming that oxidation film mostly is dielectric film greatly, the positive electrode specific capacity descends after the coating of having avoided causing thus problem; 3) LiCoO after employing the inventive method coats
2The LiCoO that the lithium ion battery that positive electrode makes is uncoated with employing
2The lithium ion battery that positive electrode makes is compared, because the mitigation that the electrochemical reaction of inside battery becomes was inviolent in the past, and have more stable charge-discharge performance, and loop attenuation also is significantly less than not and coats, and circulation later stage battery capacity remain unchanged substantially (seeing embodiment two).Provided by the invention to LiCoO
2Method for modified cladding and the battery that adopts this method to make can effectively improve or remedy LiCoO
2The defective that material is intrinsic has a good application prospect.
The invention will be further described below in conjunction with drawings and Examples, will help further to understand method of the present invention and advantage, but embodiment is only for understanding the present invention.
[description of drawings]
Below by embodiment also in conjunction with the accompanying drawings, the present invention is described in further detail:
Fig. 1 a, b are respectively LiCoO among the embodiment one
2SEM figure before and after material surface coats.
Fig. 2 a, b adopt the surface not coat and surface coated LiCoO among the embodiment two
2The charging and discharging curve figure of the lithium ion battery that material makes.
Fig. 3 a, b adopt the surface not coat and surface coated LiCoO among the embodiment two
2The cyclic curve figure of the lithium ion battery that material makes.
[embodiment]
Embodiment one, with LiOH, HBO
3, Al (NO
3)
3Be the solution of 2: 1: 1 ratio preparation 1% soluble in water in molar ratio, with the 100gLiCoO of drying
2Powder joins in the above-mentioned solution of 45g, adds the PEO solution 150g of 1% concentration, 250,000 molecular weight behind the stirring 20min again, continues to stir 30min.With 70 ℃ of heating slurries, heat while stirring then, make its water evaporates.Then with LiCoO
2Put into baking oven baking 6～8h of 60 ℃, in calciner, handle again, just obtain coated with conductive glassy layer 0.5Li of the present invention with 700 ℃, 6h
2O0.25Al
2O
30.25B
2O
3After LiCoO
2Material.Can obviously find out LiCoO after the coating by Fig. 1 a, b
2Than the LiCoO before coating
2Uniform particles, surface slyness.
Embodiment two, 0.98g LiOH is dissolved in adds 1.96g H in the 100g water again
4SiO
4Stir, add the NH of 14.3g 10% again
3H
2O is until CL.With 200g LiCoO
2Powder joins in this solution and stirs 30min, afterwards with 80 ℃ of heating evaporation moisture content.The baking oven of material being put into 80 ℃ toasts 10h again.Make the polyacrylate solution 100g of solvent preparation 3% with CMC.To expect to add in this solution and stir 40min, the heated volatile solvent.Material is put into calciner with 900 ℃, 8h processing, just obtain coated with conductive glassy layer 0.5Li of the present invention
2O0.5SiO
2After LiCoO
2Material.
Embodiment three, 1.47g LiOH is dissolved among the 100g water, adds 1.47g H again
4SiO
4Stirring adds 6.25g Al (NO afterwards until dissolving fully
3)
3Wait to dissolve the back and in this solution, add 200g LiCoO
2Powder stirs 20min, adds 10% NH
3H
2O 31g continues to stir 30min, adds 1.3% PEO solution 200g continuation stirring 30min again.Afterwards with 60 ℃ of heating evaporation moisture content.The baking oven of putting into 100 ℃ toasts about 8h, puts into calciner again with 900 ℃, 8h processing, just obtains coated with conductive glassy layer 0.5Li of the present invention
2O0.25Al
2O
30.25SiO
2After LiCoO
2Material.
Embodiment four, with 0.53g LiF, 1.18g KF, 10.77g Al (PO
3)
3Join preparation mol ratio LiF in the 100g pure water: KF: Al (PO
3)
3=1: 1: 2 solution.With LiCoO
2Powder 200g joins and stirs 20min in the solution, adds 1.6% PVA solution 100g continuation stirring 30min again.With 95 ℃ of heating evaporation moisture content, put into 90 ℃ baking oven baking 7h more afterwards.With 950 ℃, 6h calcining, just obtain coated with conductive glassy layer 0.25LiF0.25KF0.5Al (PO of the present invention then
3)
3After LiCoO
2Material.
Embodiment five, with LiOH and HPO
3Be the LiPO that is dissolved in preparation 1.1% in the 45g water at 1: 1 in molar ratio
3Solution, be LiF: LiPO more in molar ratio
3Add 0.3g LiF at=2: 1.With 100g LiCoO
2Powder joins the PVA solution that adds 100g 1% in this solution behind the stirring 20min again.Begin heating after continuing to stir 30min, heat while stirring, its water evaporates.Then with LiCoO
2Put into baking oven baking 8～9h of 60 ℃, in calciner, handle again, just obtain coated with conductive glassy layer of the present invention with 750 ℃, 8h
After LiCoO
2Material.
Copy embodiment one to five, change to generate reactant (for example LiOH, the HBO of electro-conductive glass coating layer
3, Al (NO
3)
3LiOH, H
4SiO
4LiOH, H
4SiO
4, Al (NO
3)
3LiF, KF, Al (PO
3)
3LiOH, HPO
3, LiF etc.) and reactant between mol ratio, just can obtain various general formulas is (1) XLi
2O (1-X) B
2O
3, (2) XLi
2OYAl
2O
3(1-X-Y) B
2O
3, (3) XLi
2O (1-X) SiO
2, (4) XLi
2OYAl
2O
3(1-X-Y) SiO
2, (5) XLiF (1-X) LiPO
3, (6) XLiF (1-X) Al (PO
3)
3, (7) XLiFYKF (1-X-Y) Al (PO
3)
3, (8) XLiMn
2O
4(1-X) B
2O
3, (9) XLi
2OYMnO
2-x(1-X-Y) B
2O
3, (10) are (YLi (100-X)
2SZB
2S
3) XLi
xMO
y, (11) (100-X) (YLi
2SZGeS
2) XLi
xMO
y, (12) (100-X) (YLi
2SZP
2O
5) XLi
xMO
y, (13) (100-X) (YLi
2SZSiS
2) XLi
xMO
y(10)～(13) Li in
xMO
yCan be Li
4SiO
4, Li
3PO
4, Li
4GeO
4, Li
3BO
3, Li
3AlO
3, Li
3GaO
3, Li
3InO
3Deng), (14) XAgIYAg
2O (1-X-Y) M
xO
y(M
xO
yCan be MoO
3, SeO
3, WO
3, P
2O
5, GeO
2Deng) the electro-conductive glass coating layer, 0.1≤X≤0.9 in wherein (1)～(9), 0≤Y≤(1-X), 0≤X≤0.4 in (10)～(13), 0.1＜Y＜0.9,0＜Z＜(1-Y), 0.1≤X in (14)≤0.9th, attainable span.
Embodiment six, with 1.84g Mg (NO
3)
2Be dissolved in the solution of preparation 4.1% in the 45g water.With 100g LiCoO
2Powder joins in this solution to stir and drips 25%～28% NH behind the 20min
3IH
2O 0.9g stirs the PVA solution that 20min adds 100g 1% again.Begin heating after continuing to stir 30min, heat while stirring, its water evaporates.Then with LiCoO
2Put into baking oven baking 6～8h of 60 ℃, in calciner, handle again, just obtain the LiCoO of the oxide coated MgO of the present invention with 800 ℃, 5h
2Material.
Embodiment seven, with 2.47g Fe (NO
3)
3Be dissolved in and prepare Fe (NO in the 50g water
3)
3Solution.With 100g LiCoO
2Powder joins in this solution to stir and drips excessive 25%～28% NH behind the 20min
3H
2O stirs the PEO solution (or PVA solution of 100g 1%) that 20min adds 100g 1.2% again.Begin 70～80 ℃ of heating evaporation moisture content of low temperature after continuing to stir 30min.Put it into baking oven baking 6～8h of 80 ℃ afterwards, in calciner, handle again, just obtain the oxide coated Fe of the present invention with 700 ℃, 6h
2O
3LiCoO
2Material.
The H of embodiment eight, preparation 2.1%
2SnO
3Solution 50g.With 100g LiCoO
2Powder joins in this solution to stir and adds 0.7% polypropylene pyrrolidones 100g behind the 10min again.Begin 65～75 ℃ of low-temperature heat evaporation moisture content after continuing to stir 20min.Put into 80 ℃ of baking ovens afterwards and toast 8～10h, in calciner, handle again, just obtain the oxide coated SnO of the present invention with 750 ℃, 8h
2LiCoO
2Material.
Embodiment nine, with 1.5g Na
4SiO
4Be dissolved in the 70g water, add 100g LiCoO
2Powder stirs 10min.Drip 10% HCl solution 12g again and stir 30min.Filter afterwards and refilter for 3 times with the pure water washing.Add again and heat 85 ℃ of evaporation moisture content after 1.4% soluble starch solution 100g continues to stir 30min.The baking oven of putting into 100 ℃ afterwards toasts 6h, handles in calciner with 800 ℃, 9h again, just obtains the oxide coated SiO of the present invention
2LiCoO
2Material.
Copy embodiment six to nine, adopt various bronsted lowry acids and bases bronsted lowry, salt and the alkali that generate the oxide coating film (Mg (NO for example
3)
2And NH
3H
2O), acid and salt (for example HCl and Na
4SiO
4) wait prescription just can obtain coating various oxide LiCoO
2Material, described oxide can be MgO, B
2O
3, Al
2O
3, Fe
2O
3, SiO
2, SnO
2, TiO
2, ZrO
2In a kind of.Also can carry out the coating of multiple oxide simultaneously handles.
The LiCoO that makes among embodiment ten, the employing embodiment one
2Positive electrode is made commercially available rectangular cell 053048S and test process:
1) manufacturing of positive plate: coat LiCoO with this
2. press LiCoO
2: conductive agent (super ' P '): PVdF (Kynoar): NMP (N-methyl pyrrolidone)=100: 3: 3: 55 ratios preparation anode sizing agent.At first 3 parts of PVdF are dissolved among 55 parts of NMP, high-speed stirred 1～1.5h, the back adds conductive agent continues to stir 2～2.5h, then adds the LiCoO of the coated with conductive glassy layer that makes among the embodiment one again
2Continue stir about 3h, the anode sizing agent that must prepare.Again the slurry for preparing is crossed 150 mesh sieve.Be uniformly coated on the thick aluminium foil of 20 μ m slurry is two-sided with the long medium-sized coating machine of 4m afterwards, through oven dry, cut sheet, scraping blade, compressing tablet, cut operation such as small pieces and make the 053048S battery anode slice.There is not macromolecule organic to participate in the LiCoO that coats
2Fast, the sad sieve of retrogradation knot can appear in slurry during the material batching, and pole piece has a large amount of cuts during the slurry coating, and phenomenons such as material are easily fallen in the pole piece hardening.
2) manufacturing of negative plate: with Changsha Xing Cheng graphite in graphite: SBR: CMC (sodium carboxymethylcellulose): conductive agent (super ' P ')=100: 6: 2: 1 ratio preparation cathode size.At first 2 parts of CMC are dissolved in 125 parts of pure water high speeds and stir 1～1.5h, add 6 parts of SBR again and continue to stir 1～1.5h, stir 1～1.5h again behind the adding conductive agent, add graphite at last and stir 2.5～3h, the cathode size that must prepare.With 100 mesh sieve slurry is sieved.Afterwards with the long medium-sized slurry coating machine of 4m with on the two-sided copper platinum that is uniformly coated on 12 μ m of slurry, through oven dry, cut sheet, cut small pieces, operations such as scraping blade, compressing tablet make the 053048S battery cathode sheet.
3) assembled battery: positive plate, negative plate and the lithium battery diaphragm paper (Ube) of above-mentioned made battery are wound on together with common process.Make battery 053048S through operations such as flattening, wrap electric core, go into shell, nickel strap spot welding, cover plate location, Laser Welding, fluid injection, preliminary filling, steel ball are sealed afterwards.
4) detection of battery: carry out preliminary filling again with placing 4h behind the above-mentioned 053048S battery injection 2.2g～2.4g electrolyte that makes.Priming procedure is for " (C is a multiplying power, and 0.05C has represented the current charges with 0.05 multiplying power with 0.05C.) current charges 60min, again with 0.1C current charges 50min, at last with 0.2C current charges 165min ".Finish behind the preliminary filling with steel ball battery seal, again battery is changed into afterwards.Change into step for the 0.5C electric current with battery charge to 4.2V, afterwards with the 1C current discharge to 3.0V.Finish after first circulation, to 4.2V, transfer constant voltage 4.2V charging 60min again to the 1C current charges, afterwards with the 1C current discharge to 2.75V.Finish after second circulation with the 0.2C current charges to 3.75V, must 053048S finished product battery.Follow the electrical property of test product 053048S battery.Testing procedure charges to electric current less than 30mA for transferring to constant voltage 4.2V to the 4.2V with the 1C current charges, place after the 5min with the 1C current discharge to 2.75V, place 5min again, so far battery is just finished a test loop, has just finished the test of battery 053048S for 10 times with this step cycle.By the LiCoO that does not coat
2The charging and discharging curve figure of the battery that positive electrode is made and battery cyclic curve figure see Fig. 2 a, Fig. 3 a.LiCoO by the present invention's coating
2The charging and discharging curve figure of the 053048S battery that positive electrode is made and battery cyclic curve figure see Fig. 2 b, Fig. 3 b.Comparison diagram 2a, b can find out uncoated LiCoO
2The platform of charging and discharging curve obviously little than what coated, and the platform gradient is steep.LiCoO after this explanation coats
2Material more stable than before coating when discharging and recharging.The mitigation that the electrochemical reaction of inside battery becomes was inviolent in the past.See cyclic curve Fig. 3 a, b again, coat LiCoO
2Advantage just more obvious.LiCoO through coating
2Not only capacity performance is than the height that does not coat, and loop attenuation also is significantly less than and do not coat, and circulation later stage battery capacity remains unchanged substantially.Relatively more provided by the invention from many ways to LiCoO
2Method for modified cladding effectively improve really or remedied LiCoO
2The defective that material is intrinsic.
Claims (9)
1, a kind of compound is characterized in that: at LiCoO
2The dusty material surface is coated with conductive glass layer.
2, compound according to claim 1 is characterized in that: described electro-conductive glass is
1)XLi
2O·(1-X)B
2O
3；
2)XLi
2O·YAl
2O
3·(1-X-Y)B
2O
3；
3)XLi
2O·(1-X)SiO
2；
4)XLi
2O·YAl
2O
3·(1-X-Y)SiO
2；
5)XLiF·(1-X)LiPO
3；
6)XLiF·(1-X)Al(PO
3)
3；
7)XLiF·YKF·(1-X-Y)Al(PO
3)
3；
8)XLiMn
2O
4·(1-X)B
2O
3；
9)XLi
2O·YMnO
2-x·(1-X-Y)B
2O
3；
10)(100-X)(YLi
2S·ZB
2S
3)·XLi
xMO
y；
11)(100-X)(YLi
2S·ZGeS
2)·XLi
xMO
y；
12)(100-X)(YLi
2S·ZP
2O
5)·XLi
xMO
y；
13)(100-X)(YLi
2S·ZSiS
2)·XLi
xMO
y；
14)XAgI·YAg
2O·(1-X-Y)M
xO
y；
In any one, wherein: 1)～9) in 0.1≤X≤0.9,0≤Y≤(1-X); 10) 0≤X～13)≤0.4,0.1＜Y＜0.9,0＜Z＜(1-Y), Li
xMO
y=Li
4SiO
4, Li
3PO
4, Li
4GeO
4, Li
3BO
3, Li
3AlO
3, Li
3GaO
3, Li
3InO
314) 0.1≤X in≤0.9, M
xO
y=MoO
3, SeO
3, WO
3, P
2O
5, GeO
2
3, anode material for lithium-ion batteries LiCoO
2Method for modified cladding, comprise the steps:
1) with LiCoO
2Powder with can be at LiCoO
2The surface solution that generates oxide or conductive glass surface coating layer mix and stir;
2) when carrying out step 1) or after carrying out step 1), also add high-molecular organic material solution;
3) said mixture is obtained the surface through coating the LiCoO that handles after dewatering, toast, calcining
2
4, anode material for lithium-ion batteries LiCoO according to claim 3
2Method for modified cladding, it is characterized in that: described high-molecular organic material solution is one or more the aqueous solution in polyvinyl alcohol, polyethylene glycol oxide, polyacrylamide, polytetrafluoroethylene, polypropylene pyrrolidones, butadiene-styrene rubber, the soluble starch; Or the bipolymer of polyvinylidene fluoride resin, vinylidene and hexafluoropropylene, one or more organic solvents in the low molecular weight polyacrylate.
5, anode material for lithium-ion batteries LiCoO according to claim 4
2Method for modified cladding, it is characterized in that: the quality percentage composition of the aqueous solution of described high-molecular organic material is 0.1% to 5%.
6, according to any described anode material for lithium-ion batteries LiCoO of claim 3～5
2Method for modified cladding, it is characterized in that: described oxide is MgO, B
2O
3, Al
2O
3, Fe
2O
3, SiO
2, SnO
2, TiO
2, ZrO
2In at least a.
7, according to any described anode material for lithium-ion batteries LiCoO of claim 3～5
2Method for modified cladding, it is characterized in that: described electro-conductive glass is
1)XLi
2O·(1-X)B
2O
3；
2)XLi
2O·YAl
2O
3·(1-X-Y)B
2O
3；
3)XLi
2O·(1-X)SiO
2；
4)XLi
2O·YAl
2O
3·(1-X-Y)SiO
2；
5)XLiF·(1-X)LiPO
3；
6)XLiF·(1-X)Al(PO
3)
3；
7)XLiF·YKF·(1-X-Y)Al(PO
3)
3；
8)XLiMn
2O
4·(1-X)B
2O
3；
9)XLi
2O·YMnO
2-x·(1-X-Y)B
2O
3；
10)(100-X)(YLi
2S·ZB
2S
3)·XLi
xMO
y；
11)(100-X)(YLi
2S·ZGeS
2)·XLi
xMO
y；
12)(100-X)(YLi
2S·ZP
2O
5)·XLi
xMO
y；
13)(100-X)(YLi
2S·ZSiS
2)·XLi
xMO
y；
14)XAgI·YAg
2O·(1-X-Y)M
xO
y；
In any one, wherein: 1)～9) in 0.1≤X≤0.9,0≤Y≤(1-X); 10) 0≤X～13)≤0.4,0.1＜Y＜0.9,0＜Z＜(1-Y), Li
xMO
y=Li
4SiO
4, Li
3PO
4, Li
4GeO
4, Li
3BO
3, Li
3AlO
3, Li
3GaO
3, Li
3InO
314) 0.1≤X in≤0.9, M
xO
y=MoO
3, SeO
3, WO
3, P
2O
5, GeO
2
8, a kind of anode material for lithium-ion batteries is characterized in that: described anode material for lithium-ion batteries is made by the described method of claim 3～7.
9, a kind of lithium ion battery comprises positive plate, it is characterized in that: described positive plate is made by the described anode material for lithium-ion batteries of claim 8.
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|---|---|---|---|
| CNB2004100816641A CN100377391C (en) | 2004-12-29 | 2004-12-29 | Method for modified cladding composite, anode material LiCoO* of lithium ion battery, and batteries |
| HK06110876A HK1088996A1 (en) | 2004-12-29 | 2006-09-29 | An improved coating method of a compound, anode material of li-ion battery licoo2 and battery thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100816641A CN100377391C (en) | 2004-12-29 | 2004-12-29 | Method for modified cladding composite, anode material LiCoO* of lithium ion battery, and batteries |
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| CN1797822A true CN1797822A (en) | 2006-07-05 |
| CN100377391C CN100377391C (en) | 2008-03-26 |
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| HK (1) | HK1088996A1 (en) |
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2004
- 2004-12-29 CN CNB2004100816641A patent/CN100377391C/en active Active
-
2006
- 2006-09-29 HK HK06110876A patent/HK1088996A1/en not_active IP Right Cessation
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| CN100377391C (en) | 2008-03-26 |
| HK1088996A1 (en) | 2006-11-17 |
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