CN102386439B - Lithium ion secondary battery - Google Patents
Lithium ion secondary battery Download PDFInfo
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- CN102386439B CN102386439B CN201010274846.6A CN201010274846A CN102386439B CN 102386439 B CN102386439 B CN 102386439B CN 201010274846 A CN201010274846 A CN 201010274846A CN 102386439 B CN102386439 B CN 102386439B
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- 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 belongs to the technical field of batteries, and in particular discloses a lithium ion secondary battery. The lithium ion secondary battery comprises a battery shell, a pole core and an electrolyte, wherein the pole core and the electrolyte are hermetically accommodated in the battery shell; the pole core comprises an anode, a cathode and a diaphragm; the anode and the cathode comprise current collectors and anode and cathode materials; the electrolyte comprises a lithium salt, an organic solvent and an additive; the cathode material comprises a carbon material and a silicon nano wire; and the negative ions in the lithium salt are selected from one or more of perfluoroalkyl negative ions, chelate boron negative ions, organic aluminate negative ions, chelate phosphorus negative ions, perfluoro-phosphine negative ions, imido negative ions and silicon amido negative ions. Compared with the conventional silicon nano wire battery, the lithium ion secondary battery has the advantages that: the cycle performance of the battery is greatly improved, so that the service life of the battery is greatly prolonged.
Description
Technical field
The invention belongs to battery technology field, relate in particular to a kind of lithium rechargeable battery.
Background technology
At present, the negative pole of lithium rechargeable battery adopts graphite-like material with carbon element more, but its theoretical specific capacity is low.Silicon materials enjoy industry to pay close attention to its huge theoretical lithium storage content.Lithium can obtain different alloy products from pasc reaction, as Li
12si
17, Li
13si
4, Li
7si
3, Li
22si
5deng, the alloy Li forming when wherein Si embeds lithium
4.4si, more than its theoretical capacity reaches 4200mAh/g, in the various alloys of research at present, theoretical capacity is the highest.
But silicon materials are in charge and discharge cycles process, the reversible generation of Li-Si alloy is accompanied by huge change in volume (reaching 400%) with decomposition, can cause the mechanical disintegration (producing crack and efflorescence) of alloy, cause the avalanche of material structure and peeling off of electrode material and electrode material lost electrically contacting, thereby cause the cycle performance of electrode sharply to decline, finally cause electrode failure.
At present, silicon nanowires is due to its one-dimentional structure, and in embedding lithium process, it has enough volumetric expansion spaces, thereby can bear compared with large swelling stress and not efflorescence.In addition, silicon nanowires directly contacts with collector, has guaranteed the continuous of lithium ion radial diffusion, thereby good electronics path is provided and has shortened lithium ion diffusion length.Silicon nanowires can also bear larger stress and plastic deformation, aspect toughness of material, also improves a lot.But, adopt silicon nanowires as negative material, the cycle performance of battery or not ideal enough.
Summary of the invention
Technical problem to be solved by this invention is: in prior art, adopt silicon nanowires as the bad problem of the cycle performance of lithium ion battery of negative pole; Provide a kind of cycle performance good lithium rechargeable battery.
, it comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in battery case;
Described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and described positive pole comprises collector and load on the positive electrode on collector, and described negative pole comprises collector and loads on the negative material on collector;
Described electrolyte comprises lithium salts, organic solvent;
Wherein, described negative material comprises material with carbon element and silicon nanowires; In described lithium salts, anion is selected from one or more in perfluoroalkyl anion, chelating boron anion, organo-aluminium acidic group anion, chelating phosphorus anion, perfluor phosphine anion, imido grpup anion and silica-based amido anion.
Lithium rechargeable battery provided by the present invention, compares existing silicon nanowires battery, and its cycle performance of battery has had significantly raising, thereby has greatly extended the useful life of battery.
Accompanying drawing explanation
Fig. 1 is the SEM figure (2 μ m) of one embodiment of the invention negative material.
Fig. 2 is the SEM figure (5 μ m) of one embodiment of the invention negative material.
Embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
, it comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in battery case;
Described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and described positive pole comprises collector and load on the positive electrode on collector, and described negative pole comprises collector and loads on the negative material on collector;
Described electrolyte comprises lithium salts, organic solvent;
Wherein, described negative material comprises material with carbon element and silicon nanowires; In described lithium salts, anion is selected from one or more in perfluoroalkyl anion, chelating boron anion, organo-aluminium acidic group anion, chelating phosphorus anion, perfluor phosphine anion, imido grpup anion and silica-based amido anion.
In lithium rechargeable battery of the present invention, positive pole is not had to specific (special) requirements, positive pole can be positive pole common in lithium rechargeable battery.
In the present invention, the collector in positive pole is known in those skilled in the art, and therefore not to repeat here.
Positive electrode is also known in those skilled in the art, generally comprises cobalt nickel manganese series, series of phosphate, titanium series, vanadium serial etc.Common positive electrode has: lithium cobalt oxygen LiCoO
2, lithium nickel oxygen LiNiO
2, lithium manganese oxygen LiMnO
2, lithium-nickel-cobalt-oxygen, lithium nickel cobalt manganese oxygen, LiFePO
4, Li
3v
2(PO
4)
3, LiMnPO
4, Li
2feSiO
4, Li
2mnSiO
4, LiVO
2, Li
2v
2o
4, LiV
3o
8and above-mentioned substance is coated or the product of doping.
The present invention preferably includes LiCoO
2, LiMnO
2, LiNiO
2, Li (Ni
0.8co
0.2) O
2, LiNi
1/3co
1/3mn
1/3o
2, LiFePO
4, Li
3v
2(PO
4)
3, LiV
3o
8in one or more.
In positive pole, binding agent and conductive agent are known in those skilled in the art, and therefore not to repeat here.
Anodal preparation method is uniformly mixed positive electrode, conductive agent and binding agent by a certain percentage and obtains required anode sizing agent in solvent, then by this slurry coating on collector, through super-dry, compressing tablet, process and obtain anodal.
The present invention can be selected from the conventional solvent using in this area for positive electrode solvent, as being selected from 1-METHYLPYRROLIDONE (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and alcohols.The consumption of solvent can be coated on described collector described slurry.In general, the consumption of solvent is that to make the concentration of positive electrode in slurries be 40～90wt%, is preferably 50～85wt%.
In lithium rechargeable battery of the present invention, negative pole comprises collector and loads on the negative material on collector.This negative material comprises material with carbon element and silicon nanowires, and material with carbon element is graininess, and silicon nanowire distribution is on described material with carbon element;
Wherein, silicon nanowires is material known in those skilled in the art.It is one-dimentional structure, can, by commercially available, also can oneself prepare.
Silicon nanowires of the present invention can be the silicon nanowires of whole crystal structures, can also be to be all the silicon nanowires of amorphous silicon, can be more that surface is amorphous silicon, and inside is the silicon nanowires of the nucleocapsid structure of crystal structure.
Under preferable case, the average diameter of silicon nanowires of the present invention is 10～120nm, and length is 1～20 μ m.More preferably average diameter is 20～80nm, and length is 2～10 μ m.
Wherein, material with carbon element is also material known in those skilled in the art.
Material with carbon element of the present invention is preferably selected from one or more in graphite, hard carbon, soft carbon and graphitized intermediate-phase carbon microballon MCMB; Graphite more preferably.
The preferred material with carbon element of the present invention is graininess, and silicon nanowires is coated on material with carbon element.
The microscopic appearance of material with carbon element can be spherical, class is spherical or laminar structured.
Under preferable case, the median particle diameter D of material with carbon element of the present invention
50be 2～20 μ m, 5～15 μ m more preferably.
In the present invention, the mass ratio of silicon nanowires and material with carbon element is 1: 99～50: 50, more preferably 2: 98～20: 80.Can make like this capacity of battery and cycle performance all in higher level.
In negative pole, also comprise negative pole binding agent, negative pole binding agent is negative pole binding agent conventionally known to one of skill in the art.Negative pole binding agent of the present invention can be selected from one or more in polythiophene, polypyrrole, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, polyacrylamide, ethylene-propylene-diene copolymer resins, styrene butadiene ribber, polybutadiene, fluorubber, Pluronic F-127, polyvinylpyrrolidone, mylar, acrylic resin, phenolic resins, epoxy resin, polyvinyl alcohol, carboxy-propyl cellulose and ethyl cellulose.
Negative pole of the present invention can also optionally contain common contained conductive agent in prior art negative pole.Due to the conductivity of conductive agent for increasing electrode, reduce the internal resistance of battery, so the present invention preferably contains conductive agent.The content of described conductive agent and kind are conventionally known to one of skill in the art, for example, take negative material as benchmark, and the content of conductive agent is generally 0.1～12wt%.Described conductive agent can be selected from one or more in conductive carbon black, carbon nano-tube, nickel powder, copper powder.
According to the difference of binding agent kind used, the weight of negative material of take is benchmark, and the content of negative pole binding agent is 0.01～10wt%, is preferably 0.02～5wt%; The content of conductive agent is 0～12wt%, is preferably 2～10wt%.
The preparation technology of negative pole is uniformly mixed negative material, binding agent by a certain percentage and obtains required cathode size in solvent, then by this slurry coating on collector, through super-dry, compressing tablet, process and obtain negative pole.The normal solvent adopting is 1-METHYLPYRROLIDONE (NMP), water, ethanol, acetone etc., take negative material as benchmark, and the consumption of solvent is 50-400%.
In lithium rechargeable battery of the present invention, barrier film is arranged between positive pole and negative pole, has electrical insulation capability and liquid retainability energy.Described barrier film can be selected from and well known to a person skilled in the art various barrier films used in lithium rechargeable battery, for example polyolefin micro porous polyolefin membrane (PP), polyethylene felt (PE), glass mat or ultra-fine fibre glass paper or PP/PE/PP.Described barrier film can be also polyimide film.Described polyimide film can be polyimide film known in those skilled in the art, and preferably its porosity is 20%～55%, and average pore diameter is 30～120nm.
In lithium rechargeable battery of the present invention, in electrolyte, contain lithium salts, organic solvent.
Wherein, in electrolyte, the anion of lithium salts is selected from one or more in anion:
Alkyl sulfonic acid anion, perfluoroalkyl anion, chelating boron anion, organo-aluminium acidic group anion, chelating phosphorus anion, perfluor phosphine anion, imido grpup anion and silica-based amido anion.
Under preferable case, lithium salts of the present invention is selected from LiB (C
2o
4)
2, Li
2al (CSO
3cl
4), LiP (C
6h
4o
2)
3, LiPF
3(C
2f
5)
3and LiN (SiC
3h
9)
2in one or more.
The concentration of the preferred lithium salts of the present invention is for being 0.3～3mol/L, more preferably 0.5～1.5mol/L.
Organic solvent in electrolyte of the present invention can adopt the conventional solvent in this area, EC (vinyl carbonate) for example, PC (propylene carbonate), FEC (fluorinated ethylene carbonate), DEC (diethyl carbonate), DMC (dimethyl carbonate), EMC (ethyl-methyl carbonic ester), DME (dimethoxy-ethane), GBL (gamma-butyrolacton), DMC (dimethyl carbonate), MF (methyl formate), MA (methyl acrylate), MB (methyl butyrate), EP (ethyl acetate), ES (ethylene sulfite), PS (propylene sulfite), DMS (methyl sulfide), DES (diethyl sulfite) etc.
One or more in optimal ethylene carbonic ester of the present invention, propylene carbonate, fluorinated ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester.
In electrolyte of the present invention, also preferably contain additive, additive can be selected additive known in those skilled in the art.
The preparation method of lithium rechargeable battery of the present invention, carries out according to method as well known to those skilled in the art.In general, the method comprises positive pole, negative pole and the barrier film between positive pole and negative pole is reeled successively or stacked formation pole piece, and pole piece is inserted in battery case, add electrolyte, then sealing, wherein, the method for coiling and sealing is that those skilled in the art are known.The consumption of electrolyte is conventional amount used.
The present inventor is through a large amount of experimental studies and analyze discovery, cause the bad reason of silicon nanowires cycle performance of battery in prior art mainly: the surface of silicon nanowires inevitably exists the oxide of certain silicon, the oxide of silicon can change surface state character and the surface charge of silicon nanowires, thus guaranteed silicon nanowires can stable existence in air.But the oxide of this silicon can react with the anion of lithium salts in electrolyte of the prior art, thereby lithium salts is decomposed.With the most frequently used LiPF
6for example, LiPF
6in battery, there is following balance:
LiPF
6＝LiF+PF
5，
And 2PF
5+ SiO
2=SiF
4↑+2PF
3o
Thereby cause LiPF
6and the reaction of the last decomposition of other similar inorganic lithium salts, from affecting the performance of electrolyte.Meanwhile, while changing into due to above-mentioned reaction continue carry out, be unfavorable for forming on the surface of silicon nanowires SEI film.Thereby have a strong impact on the cycle performance of silicon nanowires battery.Secondly, the factor that affect silicon nanowires cycle performance of battery also has: the electronic conductivity of silicon nanowires itself is low, and silicon nanowires easily lumps in charge and discharge process, can aggravate electronic conductivity reduction.
The present inventor surprisingly finds: silicon nanowire material is distributed in material with carbon element, adopts lithium salts of the present invention in electrolyte, the cycle performance of battery has had significantly raising.
The reason that the present inventor infers is: in the present invention, the organic anion of lithium salts, for silicon nanowires, has good chemical stability; Thereby can effectively suppress the boundary response between silicon nanowires and electrolyte, and be conducive to form stable interfacial film SEI film on silicon nanowires.Meanwhile, organic anion has larger ionic radius, the electric charge of anion can be carried out to delocalization, thereby reduces lattice energy, reduces the interaction between ion, has guaranteed dissolubility and conductivity.Silicon nanowire distribution of the present invention on material with carbon element, the caking phenomenon of silicon nanowires in the time of on the one hand can effectively suppressing to discharge and recharge; On the other hand, material with carbon element is good electronic conductor, can make up the problem of the electronic conductivity of silicon nanowires.Thereby the conductivity that makes negative material has had significantly raising.Finally cause the raising of cycle performance of battery.
Below in conjunction with specific embodiment, the invention will be further elaborated.
Embodiment 1
(1) anodal making:
By 940gLiCoO
2, 30g PVDF, 30g conductive agent acetylene black join in 600g solvent NMP, then in de-airing mixer, stirs, and forms the anode sizing agent of stable uniform.This slurry is intermittently coated on the two sides of aluminium foil (aluminium foil is of a size of: width 160mm, thickness 16 μ m) equably, and then 120 ℃ of oven dry, after roll squeezer compressing tablet, cut out as being of a size of the pole piece of 480mm*45mm and obtain anode pole piece.
(2) making of negative pole:
First 1000g deionized water is joined in 60g silicon nanowires, ultrasonic wave disperses 60min to the disappearance of floccule mass aggressiveness, then adds while stirring 940g graphite (Japanese NCK, D
50=15 μ m), after graphite all adds, add binding agent CMC solution (wherein CMC content is 60g); Stir and ultrasonic wave dispersion 120min simultaneously, add a certain amount of solvent adjustment slurry viscosity to 2000～3000cp, obtain electrode slurry.This slurry is intermittently coated on the two sides of Copper Foil (aluminium foil is of a size of: width 160mm, thickness 16 μ m) equably, and then 120 ℃ of oven dry, after roll squeezer compressing tablet, cut out as being of a size of the pole piece of 480mm*45mm and obtain cathode pole piece.
(3) preparation of electrolyte
EC: DEC is usingd to mixing that volume ratio is 4: 6 ratios as solvent, then by electrolyte lithium salt LiN (SiC
3h
9)
2be dissolved in solvent, add a certain amount of additive, prepare electrolyte.Wherein, in electrolyte, the concentration of lithium salts is 1mol/L.
(4) making of battery
Between the positive plate of above-mentioned preparation, negative plate, arrange PP/PE/PP barrier film by reeling, sheath body, inject above-mentioned electrolyte, seal, change into etc. makes battery, is denoted as A1.
Embodiment 2
With embodiment 1 difference be: electrolyte lithium salt is LiPF
3(C
2f
5)
3, the lithium salt in electrolyte is 1.5mol/L, other parts are with embodiment 1.The battery of making, is denoted as A2.
Embodiment 3
With embodiment 1 difference be: electrolyte lithium salt is LiBC
2o
4f
2, the lithium salt in electrolyte is 0.5mol/L, other parts are with embodiment 1.The battery of making, is denoted as A3.
Embodiment 4
With embodiment 1 difference be: electrolyte lithium salt is LiB (C
2o
4)
2, the lithium salt in electrolyte is 0.8mol/L, he is partly with embodiment 1.The battery of making, is denoted as A4.
Embodiment 5
With embodiment 1 difference be: electrolyte lithium salt is LiN (SiC
3h
9)
2and LiB (C
2o
4)
2, LiN (SiC in electrolyte
3h
9)
2concentration be 0.6mol/L, LiB (C
2o
4)
2for 0.4mol/L.Other parts are with embodiment 1.The battery of making, is denoted as A5.
Embodiment 6
With embodiment 5 differences be: the amount of the silicon nanowires in negative material is 100g, graphite is 900g.Other parts are with embodiment 1.The battery of making, is denoted as A6.
Embodiment 7
With embodiment 5 differences be: the amount of the silicon nanowires in negative material is 150g, graphite is 850g.Other parts are with embodiment 1.The battery of making, is denoted as A7.
Embodiment 8
With embodiment 5 differences be: the amount of the silicon nanowires in negative material is 40g, graphite is 960g.Other parts are with embodiment 1.The battery of making, is denoted as A8.
Comparative example 1
With embodiment 1 difference be:
The making of step (2) negative pole: first 1000g solvent deionized water is joined in 200g silicon nanowire material, ultrasonic wave disperses 60min to disappear to floccule mass aggressiveness, interpolation CMC (binding agent) solution, wherein the amount of CMC is 20g; Stirring and ultrasonic wave disperse to carry out 120min simultaneously, add a certain amount of solvent adjustment slurry viscosity to 2000～3000cp, obtain electrode slurry.This slurry is intermittently coated on the two sides of Copper Foil (aluminium foil is of a size of: width 160mm, thickness 16 μ m) equably, and then 120 ℃ of oven dry, after roll squeezer compressing tablet, cut out as being of a size of the pole piece of 480mm*45mm and obtain cathode pole piece.
Other parts are with embodiment 1.The battery of making, is denoted as AC1.
Comparative example 2
With embodiment 1 difference be: use LiPF
6replace LiN (SiC
3h
9)
2, lithium salt is constant.Other parts are with embodiment 1.The battery of making, is denoted as AC2.
Performance Detection:
By the battery of A1-A8 and AC1-AC2 respectively get 50 change into, partial volume, holding up on day BS-9300 secondary cell device for detecting performance, under 23 ± 2 ℃ of conditions, battery is carried out to charge and discharge cycles test with 0.2C.Step is as follows: shelve 10min; Constant voltage charge ends to 4.2V/0.05C; Shelve 10min; Constant-current discharge is to 3.0V; Circulation above-mentioned steps.Getting its mean value inserts in table 1.
Table 1
Cycle-index when as can be seen from Table 1, the conservation rate of A1-A8 battery is 80% is compared AC1-AC2 significantly raising.Also have the capability retention after circulation 300 times, also had significantly and improved.This illustrates cycle performance of battery of the present invention, and comparing silicon nanowires battery has had significantly raising.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a lithium rechargeable battery, it comprises battery case, pole piece and electrolyte, described pole piece and electrolyte sealing are contained in battery case;
Described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and described positive pole comprises collector and load on the positive electrode on collector, and described negative pole comprises collector and loads on the negative material on collector;
Described electrolyte comprises lithium salts, organic solvent;
It is characterized in that: described negative material comprises material with carbon element and silicon nanowires; In described lithium salts, anion is selected from one or more in perfluoroalkyl anion, chelating boron anion, organo-aluminium acidic group anion, chelating phosphorus anion, perfluor phosphine anion, imido grpup anion and silica-based amido anion;
Described lithium salts is LiB (C
2o
4)
2and LiN (SiC
3h
9)
2.
2. lithium rechargeable battery according to claim 1, is characterized in that: the concentration of described lithium salts is 0.3 ~ 3mol/L.
3. lithium rechargeable battery according to claim 1, is characterized in that: the average diameter of described silicon nanowires is 20 ~ 120nm, and length is 2 ~ 10 μ m.
4. lithium rechargeable battery according to claim 1, is characterized in that: the median particle diameter of described material with carbon element is 2 ~ 20 μ m.
5. lithium rechargeable battery according to claim 1, is characterized in that: described material with carbon element is graininess, and described silicon nanowires is coated on described material with carbon element.
6. lithium rechargeable battery according to claim 1, is characterized in that: described material with carbon element is selected from one or more in graphite, hard carbon, soft carbon or graphitized intermediate-phase carbon microballon.
7. lithium rechargeable battery according to claim 6, is characterized in that: the mass ratio of described silicon nanowires and material with carbon element is 1:99 ~ 50:50.
8. lithium rechargeable battery according to claim 1, is characterized in that: described positive electrode comprises LiCoO
2, LiMnO
2, LiNiO
2, Li (Ni
0.8co
0.2) O
2, LiNi
1/3co
1/3mn
1/3o
2, LiFePO
4, Li
3v
2(PO
4)
3, LiV
3o
8in one or more.
9. lithium rechargeable battery according to claim 1, is characterized in that: described organic solvent is one or more in vinyl carbonate, propylene carbonate, fluorinated ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl-methyl carbonic ester.
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| CN104347857B (en) * | 2013-07-29 | 2017-07-07 | 华为技术有限公司 | Negative electrode of lithium ionic secondary battery and preparation method thereof, cathode pole piece of lithium ion secondary battery and lithium rechargeable battery |
| CN106941153B (en) * | 2017-01-19 | 2021-04-27 | 江永斌 | Cotton-like elemental silicon nanowire cluster/carbon composite negative electrode material and preparation method and application thereof |
| CN107768640B (en) * | 2017-10-19 | 2020-09-08 | 中国科学院过程工程研究所 | Crystalline/amorphous silicon-carbon nanowire and preparation method and application thereof |
| US10818969B2 (en) | 2018-09-27 | 2020-10-27 | University Of Maryland, College Park | Borate compounds as Li super-ionic conductor, solid electrolyte, and coating layer for Li metal battery and Li-ion battery |
| CN111834613B (en) * | 2019-04-23 | 2021-12-07 | 四川佰思格新能源有限公司 | High-capacity composite negative electrode material, preparation method and lithium ion battery |
| CN114497729A (en) * | 2020-11-12 | 2022-05-13 | 山东海科新源材料科技股份有限公司 | Lithium ion battery and electrolyte for lithium ion battery |
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| CN101350404A (en) * | 2008-09-04 | 2009-01-21 | 上海交通大学 | Lithium ion battery cathode and preparation method thereof |
| CN101684548A (en) * | 2009-03-05 | 2010-03-31 | 镇江科捷锂电池有限公司 | Method for preparing amorphous silicon nano wire and application thereof in cathode of lithium battery |
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| CN101350404A (en) * | 2008-09-04 | 2009-01-21 | 上海交通大学 | Lithium ion battery cathode and preparation method thereof |
| CN101684548A (en) * | 2009-03-05 | 2010-03-31 | 镇江科捷锂电池有限公司 | Method for preparing amorphous silicon nano wire and application thereof in cathode of lithium battery |
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