CN101271974A - Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery - Google Patents
Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery Download PDFInfo
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- CN101271974A CN101271974A CNA2007100646610A CN200710064661A CN101271974A CN 101271974 A CN101271974 A CN 101271974A CN A2007100646610 A CNA2007100646610 A CN A2007100646610A CN 200710064661 A CN200710064661 A CN 200710064661A CN 101271974 A CN101271974 A CN 101271974A
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention aims at providing a novel cathode that is of high capacity, good cycle performance and used for a non-aqueous electrolyte medium lithium ion secondary battery by doping other elements in the cathode active material Si. In order to achieve the aim, an active material containing Si and being able to intercalate/de-intercalate Li, one metallic element selected from Al and Sn which is doped in the active material Si and one non-element selected from C and O constitute a cathode plate; at the same time, the lithium ion secondary battery making use of the cathode plate is provided. The active material film is carried out with structure design and doping treatment, thus prolonging the service life of the lithium ion secondary battery.
Description
Technical field
The present invention relates to a kind of cathode pole piece that is used for lithium rechargeable battery.Particularly, the present invention relates to a kind of can be used as ion cathode material lithium have height ratio capacity, a active composite material that cycle performance is good, and the cathode pole piece of preparation thus, and the lithium rechargeable battery that comprises this cathode pole piece.
Background technology
Recently, size and weight minimizing along with portable set, the demand that battery is had high-energy-density and high power density, and, make that the requirement that obtains the lithium rechargeable battery that size is littler, weight is lighter, energy storage capability is higher, charge-discharge performance is more excellent is more urgent for improving the growth requirement of environment, requirement use large power, electrically electrical automobile etc.
The negative material of commercialization lithium ion battery uses various types of carbon-based materials, for example hard carbon, Delanium and native graphite at present.Being most widely used of graphitic carbon, carbonaceous mesophase spherules wherein, the invertibity of graphite is outstanding, has guaranteed that battery has cycle life preferably.The theoretical specific capacity of graphite generally is no more than 372mAh/g, and graphite active material density low (solid density is 2.2g/cc), and therefore capacity is low aspect the energy density of electrode.The process of traditional preparation negative pole is relatively complicated, be described as: at first prepare graphitic carbon or carbonaceous mesophase spherules powder, then add conductive agent, bonding agent and other additive therein and form slurry, utilize coating machine on copper (Cu) collector, to be coated with then, thereby form the cathode pole piece of lithium ion battery.
Silicon Si is as a kind of novel negative material, and its theoretical specific capacity (4200mAh/g) is higher than the theoretical specific capacity (372mAh/g) of graphite far away.Silicon to discharge and recharge current potential similar to graphite, discharge voltage is smooth, the platform of charging and discharging curve is lower than 0.5V (V vs Li
+/ Li).But the commercialization of Si is used and but has been subjected to certain obstruction.Two subject matters that wherein face are: 1: Si and Li in charge and discharge process
+Generation alloy/remove alloy reaction can produce bigger change in volume; 2: the another one reason is the solid amorphousization that the electrochemistry that produced in alloying process first drives.Cycle performance when causing pure Si material to use as the negative pole of lithium rechargeable battery thus is poor slightly.
DLC film or amorphous carbon film are covered negative material Si surface, can suppress anodal growth and anodal degraded of going up skeleton, thus the cycle life that prolongs the secondary cell that comprises negative pole.There is research to adopt adding that Li is not had active element as the buffering matrix, perhaps between active material and collector, apply a transition zone, be expected to improve the cycle performance of Si base negative material, in addition, modification micron or nanostructure that employing can receiving volume be expanded, utilize diverse ways to prepare compound, be contained in the Li embedding thus and take off in the embedding process larger volume variation that particle took place.But, these results of study, do not make the Si active material cycle performance be improved significantly, through tens charge and discharge cycles, the capacity attenuation situation is still relatively more serious.
Summary of the invention
The invention provides a kind of negative pole that is used for lithium rechargeable battery, and the lithium rechargeable battery that utilizes this negative pole.Compare with traditional cathode pole piece commonly used at present, this cathode pole piece is directly to be deposited on the collector electrode from raw material are disposable.This negative active core-shell material has high specific capacity, improves the energy density of existing lithium-ion battery system thus greatly.Simultaneously, the charge-discharge performance of this negative active core-shell material is able to obvious improvement.
A first aspect of the present invention provides a kind of negative material that is used for lithium rechargeable battery, comprises attracting deposits and discharging Li
+Active material Si, a kind of metallic element Sn or Al and a kind of nonmetalloid C or O is characterized in that having mixed in active material Si.It has higher specific capacity and excellent cycle performance.
Negative material described in the present invention can have multi-layer film structure, is described as: active material/C (active, invigoration effect)/active material/C...... (wherein "/" expression interface).Active material is mainly the Si material, it is characterized in that mixing in this active material Si layer being selected from a kind of metallic element of Sn or Al and being selected from C or a kind of nonmetalloid of O; For the C layer, it has impalpable structure.The crystal grain of this negative film material, size is a nanoscale.
A second aspect of the present invention provides a kind of cathode pole piece, comprising: negative material and carry copper (Cu) collector of this negative material.The surface roughness of the collector Cu paper tinsel that is adopted is 0.1-10 μ m.
A third aspect of the present invention provides a kind of lithium rechargeable battery, and it comprises and utilizes cathode pole piece of the present invention and can embed and take off embedding Li
+Anode pole piece, and place the electrolyte that is used to transmit lithium ion between positive pole and the negative pole.
Brief description of drawings
Active material/C laminated film negative pole the sectional schematic diagram of Fig. 1 on the Cu collector, preparing;
Active material/C/ active material/C laminated film negative pole the sectional schematic diagram of Fig. 2 on the Cu collector, preparing;
Fig. 3 is the electrochemical properties resolution chart of the negative material of one of embodiment of the present invention;
Fig. 4 deposits the electron scanning micrograph (SEM) of active material/C laminated film on the Cu collector for one of embodiment of the present invention;
Fig. 5 is the SEM after the plural layers of one of embodiment of the present invention carry out the electrochemical properties test;
Fig. 6 is the SEM of the film that deposits on smooth surface Cu collection liquid surface;
Fig. 7 is for being the SEM of the film that deposits on the Cu collection liquid surface of 5 μ m in surface roughness;
Fig. 8 A is the cycle performance curve comparison diagram of the thin-film material of embodiment 1-1 and comparative example 1 correspondence;
Fig. 8 B is the cycle performance curve comparison diagram of the thin-film material of embodiment 1-2 and comparative example 1 correspondence;
Fig. 8 C is the cycle performance curve comparison diagram of the thin-film material of embodiment 1-3 and comparative example 1 correspondence;
Fig. 9 is the cycle performance curve comparison diagram of the thin-film material of embodiment 2 and comparative example 2 correspondences;
Figure 10 is the cycle performance curve comparison diagram of the thin-film material of embodiment 3 and comparative example 3 correspondences;
Figure 11 A is the cycle performance curve comparison diagram of the thin-film material of embodiment 4-1 and comparative example 4 correspondences;
Figure 11 B is the cycle performance curve comparison diagram of the thin-film material of embodiment 4-2 and comparative example 4 correspondences;
Figure 11 C is the cycle performance curve comparison diagram of the thin-film material of embodiment 4-3 and comparative example 4 correspondences.
Embodiment:
Now, illustrate in greater detail the present invention with reference to specific embodiment.
Term used herein " amorphous carbon " is meant to have the carbon of impalpable structure.
The positive electrode that lithium ion battery of the present invention uses can prepare according to following method: utilize solvent such as N-first class-2-Pyrrolidone (NMP), disperse the mixture LiMO of composite oxides
2(wherein M is at least a transition metal) is as LixCoO
2, LixNiO
2, LiMn
2O
4, LixMnO
3Deng, use electric conducting material such as carbon black and binding agent such as Kynoar (PVDF) simultaneously, adopt the mixture that forms to apply such as above the aluminum foil current collector.
Can make lithium ion battery of the present invention according to following method: in the air ambient or inert gas environment of drying, lamination cathode pole piece and anode pole piece, the placing porous film is as barrier film between cathode pole piece and anode pole piece.Perforated membrane can be by polyolefin, for example polypropylene or polyethylene etc.With negative pole, barrier film, anodal laminated construction, be placed in the battery container.The electrolyte that is fit to comprises the lithium salts that is dissolved in the solvent, and solvent comprises propylene carbonate, ethylene carbonate, butylene carbonate etc.And can utilize solid polymer electrolyte to replace above-mentioned liquid electrolyte.Electrolyte also can be in gel state.
The present invention can utilize magnetron sputtering technique, has prepared the negative material film with sandwich construction.Process is as follows: utilize Si target, graphite target as target respectively, the Cu paper tinsel is as collector, at Ar or Ar and CH
4, C
2H
2Deng the mist work atmosphere in, deposition Si/C layer alternate material film on the Cu paper tinsel according to process stipulation, can deposit two layers, four layers thin-film material successively.Fig. 1-Fig. 2 is respectively 2 layers of single sided deposition at the Cu paper tinsel, the sectional schematic diagram of 4 layer films.Film thickness is as follows: the Si layer thickness is no more than 10000nm; The thickness of nanometer carbon-coating is no more than 1000nm.Can utilize AlSi alloy, Al, Sn etc. to replace Si.
As reference electrode, under room temperature (25 ℃) condition, tested the chemical property of thin-film material, the charging and discharging currents density 1mA/cm that is adopted with Li with different numbers of plies
2Fig. 3 correspondence be the indicatrix that discharges and recharges of 4 layers of Si/C film.
Fig. 4-Figure 7 shows that surface topography of the negative material film of deposition.As can be seen from Figure 4, negative material combines closely with the substrate of Cu paper tinsel, the configuration of surface of massif shape, and the space has been reserved in the volumetric expansion and the contraction of taking off to active material in the process of embedding Li, has improved cycle performance.Figure 5 shows that sample through the surface topography behind the electrochemistry loop test, particle contacts still well with substrate as can be seen, and the existence of a small amount of crack is arranged, and is due to the stress that produces in the charge and discharge cycles process.From Fig. 6-Fig. 7 as can be seen, use two kinds of Cu paper tinsels: smooth Cu paper tinsel, coarse Cu paper tinsel are during as collector, and Chen Ji film morphology has than big difference thereon.In charge and discharge process, alloy film material generally has bigger volumetric expansion.And the matsurface of selection electrolysis Cu paper tinsel is as matrix, on this, carry out depositing of thin film, can increase the adhesion of film and collector, for the change in volume that embeds, takes place when taking off embedding Li provides cushion space, improve the chemical property of Si based film material to a certain extent simultaneously in charge and discharge process.
Embodiment 1-1
Utilize radiofrequency magnetron sputtering technology, simultaneously with crystal SiAl piece together target, graphite target is a target, at thickness be to deposit Si on the Cu paper tinsel of 15 μ m
xAl
yC
z/ C/Si
xAl
yC
z/ C laminated film, deposition Si
xAl
yC
zDuring layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 200W, and gas Ar flow is 58sccm.Sputtering power when depositing amorphous C rete is 400W, and gas Ar flow is 36sccm, and gained laminated film each several part thickness distribution is 500nm/50nm/500nm/50nm, and wherein in the active material rete, the atomic ratio of Si: Al: C is about 100: 50: 20.Gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Embodiment 1-2
Utilize radiofrequency magnetron sputtering technology, simultaneously with crystal SiAl piece together target, graphite target is a target, at thickness be to deposit Si on the Cu paper tinsel of 15 μ m
xAl
yC
z/ C/Si
xAl
yC
z/ C laminated film, deposition Si
xAl
yC
zDuring layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 150W, and gas Ar flow is 58sccm.Sputtering power when depositing amorphous C rete is 400W, and gas Ar flow is 36sccm, and gained laminated film each several part thickness distribution is 500nm/50nm/500nm/50nm, and wherein in the active material rete, the atomic ratio of Si: Al: C is about 100: 50: 5.Gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Embodiment 1-3
Utilize radiofrequency magnetron sputtering technology, simultaneously with crystal SiAl piece together target, graphite target is a target, at thickness be to deposit Si on the Cu paper tinsel of 15 μ m
xAl
yC
z/ C/Si
xAl
yC
z/ C laminated film, deposition Si
xAl
yC
zDuring layer, SiAl target as sputter power is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 58sccm.Sputtering power when depositing amorphous C rete is 400W, and gas Ar flow is 36sccm, and gained laminated film each several part thickness distribution is 500nm/50nm/500nm/50nm, and wherein in the active material rete, the atomic ratio of Si: Al: C is about 100: 1: 1.Gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Comparative example 1
Utilizing radiofrequency magnetron sputtering technology, is target with crystal Si target, graphite target simultaneously, is deposition Si/C/Si/C laminated film on the Cu paper tinsel of 15 μ m at thickness, and the sputtering power of Si target is 500W during deposition Si rete, and gas Ar flow is 58sccm.Sputtering power when depositing amorphous C rete is 400W, gas Ar flow is 36sccm, gained laminated film each several part thickness distribution is 500nm/50nm/500nm/50nm, and gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Embodiment 1-1,1-2,1-3 and comparative example 1 pairing thin film electrochemistry cycle performance curve this shows shown in Fig. 8 A, 8B and 8C, through element doping, make the chemical property of S i base film be improved, and cycle performance is improved.
Embodiment 2
Utilizing the magnetically controlled DC sputtering technology, is target with crystal SiAl assembly target, graphite target respectively, gas Ar, O
2Being the doping working gas, is to deposit Si on the Cu paper tinsel of 15 μ m at thickness
xAl
yO
z/ C/Si
xAl
yO
z/ C laminated film, deposition Si
xAl
yO
zDuring layer, SiAl target as sputter power is 500W, and gas Ar flow is 58sccm, O
2Flow is 15sccm..Sputtering power when depositing amorphous C rete is 400W, and gas Ar flow is 36sccm, and gained laminated film each several part thickness distribution is 500nm/50nm/500nm/50nm, and wherein in the active material rete, the atomic ratio of Si: Al: O is about 100: 50: 5.Gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Comparative example 2
Utilizing the magnetically controlled DC sputtering technology, is target with crystal Si target, graphite target simultaneously, is deposition Si/C/Si/C laminated film on the Cu paper tinsel of 15 μ m at thickness, and the sputtering power of Si target is 500W during deposition Si rete, and gas Ar flow is 58sccm.Sputtering power when depositing amorphous C rete is 400W, gas Ar flow is 36sccm, gained laminated film each several part thickness distribution is 500nm/50nm/500nm/50nm, and gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Embodiment 2 and comparative example 2 pairing thin film electrochemistry cycle performance curves this shows as shown in Figure 9, through element doping, make the chemical property of Si base film be improved, and cycle performance is improved.
Embodiment 3
Utilize radiofrequency magnetron sputtering technology, respectively with crystal SiSn piece together target, graphite target is a target, at thickness be to deposit Si on the Cu paper tinsel of 15 μ m
xSn
y/ C/Si
xSn
y/ C laminated film, deposition Si
xSn
yLayer power is 500W, gas Ar flow is that the sputtering power of 78sccm. when depositing amorphous C rete is 400W, gas Ar flow is 66sccm, gained laminated film each several part thickness is respectively 500nm/50nm/500nm/50nm, gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Comparative example 3
Utilize radiofrequency magnetron sputtering technology, be target with crystal Si target, graphite target respectively, it at thickness deposition Si/C/Si/C laminated film on the Cu paper tinsel of 15 μ m, sputtering power during deposition Si rete is 500W, gas Ar flow is that the sputtering power of 78sccm. when depositing amorphous C rete is 400W, gas Ar flow is 66sccm, gained laminated film each several part thickness is respectively 1000nm/100nm, gained film cathode pole piece and metal Li form half-cell and carry out electrochemical property test, and electrolyte is 1M LiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 0.4mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Embodiment 3 and comparative example 3 pairing thin film electrochemistry cycle performance curves this shows as shown in figure 10, through the doping of element, select suitable thicknesses of layers, make the chemical property of Si base film be improved, and cycle performance is improved.
Embodiment 4-1
Utilizing the magnetically controlled DC sputtering technology, is target with crystal SiAl assembly target, graphite target, is the last deposition of coarse Cu paper tinsel (Cu paper tinsel roughness the is 0.1 μ m) Si of 12 μ m at thickness
xAl
yC
zFilm, wherein the sputtering power of SiAl target is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 60sccm, gained Si
xAl
yC
zLayer thickness is 2000nm, and gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1MLiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 1mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Embodiment 4-2
Utilizing the magnetically controlled DC sputtering technology, is target with crystal SiAl assembly target, graphite target, is the last deposition of coarse Cu paper tinsel (Cu paper tinsel roughness the is 5 μ m) Si of 12 μ m at thickness
xAl
yC
zFilm, wherein the sputtering power of SiAl target is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 60sccm, gained Si
xAl
yC
zFilm thickness is 2000nm, and gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1MLiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 1mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Embodiment 4-3
Utilizing the magnetically controlled DC sputtering technology, is target with crystal SiAl assembly target, graphite target, is the last deposition of coarse Cu paper tinsel (Cu paper tinsel roughness the is 10 μ m) Si of 12 μ m at thickness
xAl
yC
zFilm, wherein the sputtering power of SiAl target is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 60sccm, gained Si
xAl
yC
zFilm thickness is 2000nm, and gained film cathode pole piece and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1MLiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 1mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
Comparative example 4
Utilize the magnetically controlled DC sputtering technology, with crystal SiAl piece together target, graphite target is a target, at thickness be to deposit Si on the smooth Cu paper tinsel of 12 μ m
xAl
yC
zFilm, wherein the sputtering power of SiAl target is 500W, and the sputtering power of graphite target is 500W, and gas Ar flow is 60sccm, gained Si
xAl
yC
zThe thickness of film is 2000nm, and gained film and metal Li composition half-cell are carried out electrochemical property test, and electrolyte is 1MLiPF
6+ EC/DEC (volume ratio 1: 1), measuring current density is 1mA/cm
2, the charging/discharging voltage scope is at 0～2.0V.
The thin film electrochemistry cycle performance curve of embodiment 4-1,4-2,4-3 and comparative example 4 correspondences is shown in Figure 11 A, 11B and 11C.This shows to have the film that deposits on the Cu paper tinsel of rough surface, cycle performance will obviously be better than the film that deposits on the paper tinsel at smooth surface Cu, and the Cu paper tinsel that promptly has the suitable crude rugosity helps the performance of the chemical property of film.
The foregoing description has only been described embodiment, further, the invention is not restricted to above-mentioned embodiment, for a person skilled in the art, under the precondition that does not exceed the scope of the invention, can easily carry out various changes or replacement.Therefore, so suitable modification and be equal to the scope that replacement all will fall into the present invention and appended claim.
Claims (10)
1. negative material that is used for lithium rechargeable battery comprises embedding and the active material Si of removal lithium embedded ion that a kind of metallic element Sn or Al and a kind of nonmetalloid C or O is characterized in that having mixed in active material Si.
2. negative material according to claim 1 is characterized in that two kinds of doped chemicals are uniformly distributed in the active material, and the atomic ratio of active material and doped metallic elements, nonmetalloid is 100: 1: 1-100: 50: 20.
3. negative material according to claim 1 is characterized in that described active material exists with the form of film.
4. negative material according to claim 4 is characterized in that described negative material comprises multilayer, distributes wherein said "/" expression interface in active material/C/ active material/C mode.
5. negative material according to claim 4 is characterized in that the grain size in this negative material is a nanoscale.
6. negative material according to claim 5 is characterized in that the C layer in the negative material has impalpable structure.
7. negative material according to claim 5, the thickness that it is characterized in that active material layer is 1-2000nm, the thickness of C layer is 1-500nm.
8. cathode pole piece comprises: negative material that limits according to claim 1 and the collector that carries this negative material.
9. cathode pole piece according to claim 8 is characterized in that the collector that is adopted adopts Copper Foil, and the surface roughness of Copper Foil is 0.1-10 μ m.
10. a lithium rechargeable battery comprises: the cathode pole piece that claim 9 limits; The anode pole piece of the active material of embedding, removal lithium embedded ion; And place the electrolyte that is used to transmit described lithium ion between described cathode pole piece and the anode pole piece.
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|---|---|---|---|
| CNA2007100646610A CN101271974A (en) | 2007-03-22 | 2007-03-22 | Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery |
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|---|---|---|---|
| CNA2007100646610A CN101271974A (en) | 2007-03-22 | 2007-03-22 | Cathode material of lithium ion secondary battery, cathode pole piece and lithium ion secondary battery |
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| CN102054981A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Anode material doped with hydrogen and carbon elements and preparation method thereof |
| CN102054961A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Active negative pole piece and preparation method thereof |
| CN102054968A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Surface activated cathode piece |
| CN102891281A (en) * | 2012-10-18 | 2013-01-23 | 苏州晶纯新材料有限公司 | All solid-state thin film lithium ion battery cathode and preparation method thereof |
| CN103222091A (en) * | 2010-11-26 | 2013-07-24 | 日产自动车株式会社 | Si alloy-containing negative electrode active material for electrical devices |
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| CN111916753A (en) * | 2020-07-23 | 2020-11-10 | 珠海冠宇电池股份有限公司 | Negative plate and lithium ion battery comprising same |
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| CN102054961A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Active negative pole piece and preparation method thereof |
| CN102054968A (en) * | 2010-07-22 | 2011-05-11 | 中信国安盟固利动力科技有限公司 | Surface activated cathode piece |
| EP2645456A4 (en) * | 2010-11-26 | 2016-10-05 | Nissan Motor | Si alloy-containing negative electrode active material for electrical devices |
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