CN102637852A - Negative electrode of silicon film lithium ion battery and preparation method of negative electrode - Google Patents
Negative electrode of silicon film lithium ion battery and preparation method of negative electrode Download PDFInfo
- Publication number
- CN102637852A CN102637852A CN2012101228938A CN201210122893A CN102637852A CN 102637852 A CN102637852 A CN 102637852A CN 2012101228938 A CN2012101228938 A CN 2012101228938A CN 201210122893 A CN201210122893 A CN 201210122893A CN 102637852 A CN102637852 A CN 102637852A
- Authority
- CN
- China
- Prior art keywords
- thin film
- cobalt
- silicon
- negative electrode
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a negative electrode of a silicon film lithium ion battery. The preparation method comprises the following steps of: cleaning the surface of a substrate to obtain a cleaned substrate; placing the cleaned substrate into electrolyte containing cobalt ions, and electrolytically depositing a cobalt thin film on the substrate; and depositing a silicon thin film by adopting a magnetron sputtering method on the substrate deposited with the cobalt thin film to obtain the negative electrode of the silicon thin film lithium ion battery. According to the preparation method, firstly the cobalt thin film is electrolytically deposited on the substrate and then an amorphous-silicon thin film is deposited by adopting the magnetron sputtering method, and the preparation method is easy to implement and simple to operate, has strong operability and is easy to realize industrialization mass production. The invention also discloses the negative electrode of the silicon thin film lithium ion battery, comprising the substrate, the cobalt thin film deposited on the substrate, and the silicon thin film covered on the cobalt thin film, wherein the cobalt thin film realizes good supporting and buffering effects and good electrical conductivity, and the concave-convex surface of the silicon thin film covered on the cobalt thin film has a good buffering effect on volume variation, and thus the negative electrode disclosed by the invention has excellent performance.
Description
Technical field
The present invention relates to the electrode and the preparation field thereof of lithium ion battery, be specifically related to a kind of silicon thin film lithium ion battery negative electrode and preparation method thereof.
Background technology
Lithium ion battery have open circuit voltage height, energy density big, have extended cycle life, advantage such as memory-less effect, non-environmental-pollution, self discharge are little; Be widely used in portable electric appts such as mobile phone, notebook computer, video camera, and developed to fields such as electric tool, electric automobile, uninterrupted power supply (ups) Unity, space technology and national defense industry energetically.
The carbon negative pole material theoretical specific capacity of commercial applications has only 372mAh/g at present, can not satisfy the demand to the high energy density lithium ion battery.Silicium cathode materials theory specific capacity is up to 4200mAh/g, and discharge platform is low, aboundresources and environmentally friendly, therefore, the very potential negative material that substitutes carbon that becomes.But, cause silicium cathode material efflorescence forfeiture to electrically contact ability, and the conductivity of silicon own is relatively poor, makes its cycle performance and high rate capability relatively poor, has hindered its commercial applications because silicon change in volume in charge and discharge process is big.
In order to improve the cyclical stability of silicon, given play to the advantage of its high power capacity, a kind of method is that silicon and other materials is compound; Suppress or cushion the change in volume of charge and discharge process silicon; Thereby improve its cycle performance, a kind of in addition method is exactly with the silicon nanometerization, prepares nano silicon particles, nano wire, nanotube, nano belt etc.; The absolute volume that reduces it changes, thereby improves its cycle performance.But the silicon combination electrode material is owing to reduced content of active substance, causes the reduction of the capacity of silicon combination electrode material, though and cycle performance be improved, but still undesirable, and with the silicon nanometerization, preparation cost is high, is unfavorable for large-scale production.
Publication number is the preparation method that the one Chinese patent application of CN 101667638 A discloses a kind of lithium silicon alloy membrane electrode used for lithium ion battery; The preparation method is following: under argon shield; Lithium salts and silicon compound are joined in anhydrous organic solvent or the ionic liquid; Stirring and dissolving obtains the electrolyte of certain volume, and the molar concentration of silicon compound is 0.1～1.0molL in the electrolyte
-1, the molar concentration of lithium salts is 0.1～1.0molL
-1, above-mentioned electrolyte is placed two Room electrolytic cells, in 20 ℃～30 ℃ temperature ranges, under argon shield, carry out the electro-deposition of lithium silicon alloy, negative electrode is foam-metal current collector body or planar metal collector; Multiple current step technology is adopted in electro-deposition, and first step step apparent area current density is 1.5～8.0mA/cm
2, first step snap time is 600～1800 seconds, second step apparent area current density that jumps is 1.0～8.0mA/cm
2, the second step time of jumping was 3600～14400 seconds, after electro-deposition finishes, after the anhydrous organic solvent flushing, obtained a kind of lithium silicon alloy membrane electrode used for lithium ion battery.Whole process of preparation is all carried out under argon shield, and condition is harsh, and preparation cost is high, and is unfavorable for large-scale industrial production.Hinder the silicium cathode material commercially produce topmost problem be exactly in the cyclic process material efflorescence lose with collector and electrically contact; Cause its cycle performance poor; 20 circulation backs of material capability retention like embodiment 1 preparation has had only 89.5%, and cycle performance is relatively poor.
Publication number is that the one Chinese patent application of CN 102054966 A discloses the method that a kind of magnetron sputtering alternately precipitates multi-layer doping silicon fiml and amorphous carbon film composite multi-layer film cathode; May further comprise the steps: be respectively target with silicon-doped chemical and graphite; On metal substrate, precipitate amorphous carbon film and doping silicon fiml (doped chemical comprises one or more in aluminium, copper, iron, tin, the boron) respectively with magnetron sputtering technique, process the pole piece semi-finished product; Adopt the polymer coating that The tape casting, rubbing method or pyrolytic coating will contain oxide particle to be applied to the pole piece surface of semi-finished, obtain the finished product cathode pole piece.Adopt the magnetron sputtering pole piece directly on substrate, to precipitate completion by material; Improved the cycle performance of material; But because the adding of doped chemical and amorphous carbon film has reduced the content of active material silicon, thereby has reduced the energy density of battery, and this method can not effectively suppress or cushion the change in volume of silicon; The material cycle performance is not good, remains to be improved further.
Summary of the invention
The invention provides a kind of preparation method of silicon thin film lithium ion battery negative electrode, first electro-deposition cobalt thin film on substrate, magnetron sputtering deposition amorphous silicon membrane again, thereby the excellent silicon thin film lithium ion battery negative material of processability.
A kind of preparation method of silicon thin film lithium ion battery negative electrode may further comprise the steps:
1) substrate surface is cleaned the substrate after obtaining cleaning;
2) substrate after will cleaning places the electrolyte that contains cobalt ions, at the substrate deposit cobalt film that powers on;
3) obtain silicon thin film lithium ion battery negative electrode after adopting magnetron sputtering method depositing silicon film depositing on the substrate of cobalt thin film.
In the step 1), substrate can be selected conductive metal sheet for use, and substrate surface cleans also can adopt conventional method.
As preferably; Described substrate is a copper base; Substrate surface cleans and may further comprise the steps: is supersound washing 5min～10min in the diluted acid of 0.2mol/L～3mol/L with substrate in concentration, is neutral with distilled water flushing to substrate surface again, then with substrate supersound washing 5min～10min in alcohol; Vacuum drying, the substrate after obtaining cleaning.Wherein, diluted acid can be watery hydrochloric acid or dilute sulfuric acid.After substrate cleans through above-mentioned steps, can remove oxide skin(coating) and the greasy dirt of substrate surface etc. fully.
Step 2) in; As preferably, the electrolyte that contains cobalt ions comprises the solubility cobalt salt, helps crystallizing agent, pH buffer and deionized water, and the described pH value that contains the electrolyte of cobalt ions is 2～6; Generally regulate pH to 2～6 by pH value conditioning agent; Wherein, the concentration that contains solubility cobalt salt in the electrolyte of cobalt ions is 0.5mol/L～1.5mol/L, contains that to help the concentration of crystallizing agent in the electrolyte of cobalt ions be 0.2mol/L～2mol/L; Make crystal orientation preferential growth in metallic cobalt edge in the electrodeposition process, thereby form the cobalt thin film or the netted cobalt thin film of nano-array; The concentration that contains pH buffer in the electrolyte of cobalt ions is 0.1mol/L～1mol/L; PH buffer and pH value conditioning agent make the electrolyte that contains cobalt ions remain on specific pH value; The electro-deposition of cobalt thin film is remained under the acid condition of pH=2～6 carry out, thus the microscopic appearance of control cobalt thin film.
Further preferred, described solubility cobalt salt is cobalt chloride or cobalt nitrate, and the described crystallizing agent that helps is an ethylene diamine hydrochloride, and described pH buffer is a boric acid, and described pH value conditioning agent is that hydrochloric acid is or/and ammoniacal liquor.Ethylene diamine hydrochloride is soluble in water; And make cobalt in electro-deposition along the particular crystal orientation preferential growth; The pH value that boric acid helps containing in the course of reaction electrolyte of cobalt ions keeps within the specific limits; Hydrochloric acid and ammoniacal liquor are all very easily water-soluble, accurately control the pH of electrolyte, help accurately preparing the cobalt array film of different-shape.
At the power on optimum condition of deposit cobalt film of substrate be: temperature is 20 ℃～80 ℃, and current density is 0.008A/cm
2～0.06A/cm
2, sedimentation time is 120s～360s.
In the step 3), as preferably, described magnetron sputtering method may further comprise the steps: the substrate that will deposit cobalt thin film places the magnetron sputtering chamber, and adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 35sccm～45sccm, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 10min～60min.Magnetron sputtering gets amorphous silicon membrane; The change in volume of silicon keeps isotropism when discharging and recharging, and the stress ratio that silicon thin film is received is more even, and magnetron sputtering silicon thin film adhesion is big; All help improving the cycle performance of silicon; Magnetron sputtering is easy to control silicon thin film thickness in addition, can regulate the thickness of silicon thin film according to needs such as battery capacities, can control the thickness that sputtering time is regulated silicon thin film.
The present invention also provides a kind of silicon thin film lithium ion battery negative electrode; Comprise substrate, be deposited on on-chip cobalt thin film and cover the silicon thin film on the cobalt thin film; The thickness of described cobalt thin film is 500nm～3 μ m, and the thickness of described silicon thin film is 100nm～2 μ m.Described cobalt thin film is nano-cone array, nanometer mountain peak array, nanometer flower array or reticulated film, and described silicon thin film is an amorphous silicon membrane.
Compared with prior art, the present invention has following advantage:
The preparation method of silicon thin film lithium ion battery negative electrode of the present invention, first electro-deposition cobalt thin film on substrate, magnetron sputtering deposition amorphous silicon membrane again, this preparation method is easy to implement, and is easy and simple to handle, workable, is easy to large-scale industrialization production.
The silicon thin film lithium ion battery negative electrode of the present invention's preparation; Cobalt thin film has played the effect of good supporting and buffering and satisfactory electrical conductivity; Cover the concavo-convex surface of its surperficial silicon thin film change in volume has also been played good cushioning effect, thereby make silicon thin film lithium ion battery negative electrode of the present invention have excellent performance.Silicon thin film lithium ion battery negative electrode of the present invention is specially adapted in the lithium ion battery, uses the cycle performance and the high rate performance of the lithium ion battery of this negative electrode all to be significantly improved.Thereby silicon thin film lithium ion battery negative electrode of the present invention is easy to the marketization and promotes and utilize, and has broad application prospects and favorable economic benefit.
Description of drawings
Fig. 1 among the embodiment 1 at copper base power on deposit cobalt film and the X-ray diffraction spectrogram behind sputtered silicon film on the cobalt thin film;
Fig. 2 is the Raman spectrum behind sputtered silicon film on the cobalt thin film among the embodiment 1;
Fig. 3 is for depositing the stereoscan photograph of the copper base of cobalt thin film among the embodiment 1;
Fig. 4 is depositing the stereoscan photograph behind the depositing silicon film on the copper base of cobalt thin film among the embodiment 1;
Fig. 5 is for depositing on the copper base of cobalt thin film the stereoscan photograph in cross section behind the depositing silicon film among the embodiment 1;
Fig. 6 is for depositing the stereoscan photograph of the copper base of cobalt thin film among the embodiment 4.
Embodiment
Embodiment 1
1) be supersound washing 8min in the watery hydrochloric acid of 1mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 8min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 4 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 1mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.5mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1.4mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.04A/cm
2, sedimentation time is 120s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and sputtering time is 30min, obtains silicon thin film lithium ion battery negative electrode.
At last silicon thin film lithium ion battery negative electrode being taken out, at 90 ℃ of vacuumize 12h, is to electrode with the lithium sheet, and microporous polypropylene membrane (Cellgard 2300) is a barrier film, with 1: 1 ethylene carbonate of volume ratio and diethyl carbonate as solvent, with LiPF
6Be dissolved in the solvent, make electrolyte, LiPF in the electrolyte
6Concentration be 1mol/L, in the glove box under the argon gas atmosphere protection, be assembled into half-cell and test.
Embodiment 1 is as shown in Figure 1 at power on deposit cobalt film and X-ray diffraction spectrogram (XRD) behind sputtered silicon film on the cobalt thin film of copper base; The cobalt thin film of electro-deposition is the metal Co of the hexagonal simple structure of space group P63/mmc on copper base; The characteristic peak that does not occur crystalline silicon after the sputtered silicon, therefore, the silicon thin film of magnetron sputtering method deposition is an amorphous silicon; Raman spectrum among the embodiment 1 behind sputtered silicon film on the cobalt thin film is as shown in Figure 2, only corresponding to amorphous silicon at 480cm
-1The peak and do not have crystalline silicon at 520cm
-1The peak, proved that further from the silicon thin film of magnetron sputtering method deposition be amorphous silicon.As shown in Figure 3, the cobalt thin film that deposits on the copper base of cobalt thin film is the cobalt nano-array of elongated nanometer fish shape, and the surface has cataphracted concavo-convex.Fig. 4 is being for to deposit the pattern behind the depositing silicon film on the copper base of cobalt thin film, depositing on the copper base of cobalt thin film behind the depositing silicon film, one deck silicon thin film of can having seen cobalt nano-array surface coverage, and silicon film surface still has concavo-convex.As shown in Figure 5, the thickness that is deposited on the cobalt thin film on the copper base is 2.0 μ m ± 0.2 μ m, and the thickness that covers the silicon thin film on the cobalt thin film is 300nm ± 50nm, and overall film thickness is about 2.3 μ m.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film, and the thickness of cobalt thin film is 2.0 μ m ± 0.2 μ m, and the thickness of silicon thin film is 300nm ± 50nm.Described cobalt thin film is a nanometer mountain peak array, and wherein, length is 1 μ m ± 0.2 μ m at the bottom of the nanometer mountain peak, and wide is 200nm～500nm, and silicon thin film is an amorphous silicon membrane.
Electro-chemical test mainly comprise the test of many multiplying powers (at 0.1C, 0.2C, 0.5C; 1C, 2C, 3C; 0.1C discharge and recharge under the different multiplying, capacity placed in the middle representative as discharge capacity under this multiplying power is chosen in each multiplying power circulation 10 times) and loop test (0.1C discharges and recharges more than 100 times).The partial results of many multiplying power tests of the half-cell of embodiment 1 preparation sees table 1 for details.The very big raising that the heavy-current discharge performance of the silicon thin film lithium ion battery negative electrode of present embodiment 1 preparation also obtains in half-cell; Under 1C (4A/g) multiplying power, the capacity placed in the middle that this multiplying power circulation is 10 times is 1298.3mAh/g, under the 3C multiplying power; The capacity placed in the middle that this multiplying power circulation is 10 times also has 1000mAh/g; And high rate charge-discharge returns under the 0.1C multiplying power after finishing, and the capacity placed in the middle that this multiplying power circulation is 10 times can return to more than the 2000mAh/g.Loop test shows that under the 0.1C multiplying power, discharge capacity is up to 2792.5mAh/g first, and the first charge-discharge coulombic efficiency is that 83.5%, 100 circulation back specific discharge capacity still has 1883.8mAh/g.
Embodiment 2
1) be supersound washing 8min in the watery hydrochloric acid of 1mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 8min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 4 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 1mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.5mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1.4mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.02A/cm
2, sedimentation time is 120s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 30min, obtains silicon thin film lithium ion battery negative electrode.
At last silicon thin film lithium ion battery negative electrode being taken out, at 90 ℃ of vacuumize 12h, is to electrode with the lithium sheet, and microporous polypropylene membrane (Cellgard 2300) is a barrier film, with 1: 1 ethylene carbonate of volume ratio and diethyl carbonate as solvent, with LiPF
6Be dissolved in the solvent, make electrolyte, LiPF in the electrolyte
6Concentration be 1mol/L, in the glove box under the argon gas atmosphere protection, be assembled into half-cell and test.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film; The thickness of cobalt thin film is 1 μ m ± 0.1 μ m; The thickness of silicon thin film is 300nm ± 50nm; Cobalt thin film is a nanometer flower array, and petal is the flake nano cobalt, and silicon thin film is an amorphous silicon membrane.
Electro-chemical test mainly comprise the test of many multiplying powers (at 0.1C, 0.2C, 0.5C; 1C, 2C, 3C; 0.1C discharge and recharge under the different multiplying, capacity placed in the middle representative as discharge capacity under this multiplying power is chosen in each multiplying power circulation 10 times) and loop test (0.1C discharges and recharges more than 100 times).The partial results of many multiplying power tests of the half-cell of embodiment 2 preparations sees table 1 for details.Loop test shows that under the 0.1C multiplying power, discharge capacity is up to 2292mAh/g first, and 100 times circulation back specific discharge capacity still has 1833.8mAh/g, and capability retention is more than 75%.
Copper base after the cleaning in the step 1) is directly got into step 3), sputter Si film, example as a comparison.Be assembled into half-cell in the glove box of silicon thin film lithium ion battery negative electrode under the argon gas atmosphere protection with this method preparation and carry out loop test (0.1C discharges and recharges more than 100 times); Though under the 0.1C multiplying power; Discharge capacity has 2974.4mAh/g first; But capacity attenuation is fast, and 50 times circulation back capacity has only 552.7mAh/g, and circulating, capacity is merely 338.2mAh/g after 100 times.
Embodiment 3
1) be supersound washing 8min in the dilute sulfuric acid of 1mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 8min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 4 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 1mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.5mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1.4mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.02A/cm
2, sedimentation time is 120s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and bias voltage is-100V, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and the target as sputter electric current is 0.04A, and sputtering time is 60min, obtains silicon thin film lithium ion battery negative electrode.
At last silicon thin film lithium ion battery negative electrode being taken out, at 90 ℃ of vacuumize 12h, is to electrode with the lithium sheet, and microporous polypropylene membrane (Cellgard 2300) is a barrier film, with 1: 1 ethylene carbonate of volume ratio and diethyl carbonate as solvent, with LiPF
6Be dissolved in the solvent, make electrolyte, LiPF in the electrolyte
6Concentration be 1mol/L, in the glove box under the argon gas atmosphere protection, be assembled into half-cell and test.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film that the thickness of cobalt thin film is 1 μ m ± 0.1 μ m, about the thickness 600nm ± 80nm of silicon thin film.Described cobalt thin film is a nanometer flower array, and petal is the flake nano cobalt, and silicon thin film is an amorphous silicon membrane.
Electro-chemical test mainly comprise the test of many multiplying powers (at 0.1C, 0.2C, 0.5C; 1C, 2C, 3C; 0.1C discharge and recharge under the different multiplying, capacity placed in the middle representative as discharge capacity under this multiplying power is chosen in each multiplying power circulation 10 times) and loop test (0.1C discharges and recharges more than 100 times).The partial results of many multiplying power tests of the half-cell of embodiment 3 preparations sees table 1 for details.Compare with embodiment 2, because the Si film is thicker, reaction not exclusively; Many multiplying powers test shows, under the 0.1C multiplying power, the specific discharge capacity placed in the middle that this multiplying power circulation is 10 times is 1881.6mAh/g; Under the 1C multiplying power; The specific discharge capacity placed in the middle that this multiplying power circulation is 10 times is 1031.1mAh/g, returns under the 0.1C multiplying power, and the capacity placed in the middle that this multiplying power circulation is 10 times can return to more than the 1600mAh/g.
Embodiment 4
1) be supersound washing 8min in the watery hydrochloric acid of 1mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 8min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 4 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 1mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.5mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1.4mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.01A/cm
2, sedimentation time is 240s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 60min, obtains silicon thin film lithium ion battery negative electrode.
At last silicon thin film lithium ion battery negative electrode being taken out, at 90 ℃ of vacuumize 12h, is to electrode with the lithium sheet, and microporous polypropylene membrane (Cellgard 2300) is a barrier film, with 1: 1 ethylene carbonate of volume ratio and diethyl carbonate as solvent, with LiPF
6Be dissolved in the solvent, make electrolyte, LiPF in the electrolyte
6Concentration be 1mol/L, in the glove box under the argon gas atmosphere protection, be assembled into half-cell and test.
As shown in Figure 6, deposit cobalt thin film on the copper base of cobalt thin film for being the colored array of nanometer, petal is flake nano Co.The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film, and the thickness of cobalt thin film is about 1.5 μ m ± 0.15 μ m, and the thickness of silicon thin film is 300nm ± 50nm.Described cobalt thin film is a nanometer flower array, and petal is the flake nano cobalt, and silicon thin film is an amorphous silicon membrane.
Electro-chemical test mainly comprise the test of many multiplying powers (at 0.1C, 0.2C, 0.5C; 1C, 2C, 3C; 0.1C discharge and recharge under the different multiplying, capacity placed in the middle representative as discharge capacity under this multiplying power is chosen in each multiplying power circulation 10 times) and loop test (0.1C discharges and recharges more than 100 times).The partial results of many multiplying power tests of the half-cell of embodiment 4 preparations sees table 1 for details.Many multiplying powers test shows; First discharge specific capacity reaches 2285.6mAh/g under the 0.1C multiplying power; Capacity the highest under the 1C multiplying power still can reach more than the 1300mAh/g, returns under the 0.1C multiplying power, and the capacity placed in the middle that this multiplying power circulation is 10 times still can return to more than the 2000mAh/g.
Table 1 is that embodiment 1, embodiment 2, embodiment 3 and the silicon thin film lithium ion battery negative electrode of embodiment 4 preparations are tested in half-cell in the discharge capacity under the different discharge-rates (circulation is 10 times under each multiplying power, chooses capacity placed in the middle representative as discharge capacity under this multiplying power).
Table 1
| Discharge capacity (mAh/g) | 0.1C | 0.2C | 0.5C | 1C | 2C |
| Embodiment 1 | 2417.4 | 1990.9 | 1613.6 | 1298.3 | 953.3 |
| Embodiment 2 | 2032.1 | 1648.1 | 1543.8 | 1414.5 | 1215.9 |
| Embodiment 3 | 1881.6 | 1776.8 | 1321.1 | 1031.1 | 717.8 |
| Embodiment 4 | 2195.1 | 1750.0 | 1358.3 | 1135.5 | 679.9 |
Embodiment 5
1) be supersound washing 8min in rare nitric acid of 1mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 8min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 4 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 1mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.3mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1.4mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.02A/cm
2, sedimentation time is 120s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 30min, obtains silicon thin film lithium ion battery negative electrode.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film, and the thickness of cobalt thin film is 1.0 μ m ± 0.1 μ m, and the thickness of silicon thin film is 300nm ± 50nm.Described cobalt thin film is a nano-cone array, is specially the outstanding nano-porous film of taper, and silicon thin film is an amorphous silicon membrane.
Embodiment 6
1) be supersound washing 8min in the dilute sulfuric acid of 1mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 8min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 4 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 0.8mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.5mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.01A/cm
2, sedimentation time is 360s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 30min, obtains silicon thin film lithium ion battery negative electrode.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film, and the thickness of cobalt thin film is 700nm ± 100nm, and the thickness of silicon thin film is 300nm ± 50nm.Described cobalt thin film is a nano-cone array, and silicon thin film is an amorphous silicon membrane.
Embodiment 7
1) be supersound washing 8min in the watery hydrochloric acid of 1mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 8min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 3 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 0.8mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.5mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.02A/cm
2, sedimentation time is 120s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 30min, obtains silicon thin film lithium ion battery negative electrode.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film, and the thickness of cobalt thin film is 800nm ± 100nm, and the thickness of silicon thin film is 300nm ± 50nm.Described cobalt thin film is uniform nano-cone array, and silicon thin film is an amorphous silicon membrane.
Embodiment 8
1) be supersound washing 6min in the watery hydrochloric acid of 2mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 10min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 2 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 0.8mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.5mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.01A/cm
2, sedimentation time is 360s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 30min, obtains silicon thin film lithium ion battery negative electrode.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film, and the thickness of cobalt thin film is 700nm ± 100nm, and the thickness of silicon thin film is 300nm ± 50nm.Described cobalt thin film is a nano-cone array, and silicon thin film is an amorphous silicon membrane.
Embodiment 9
1) be supersound washing 8min in the watery hydrochloric acid of 1mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 8min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with CoCl
26H
2O, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride, through with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor adjusting pH to 5 of weight percentage 10%, obtain containing the electrolyte 60ml of cobalt ions again, wherein, contain CoCl in the electrolyte of cobalt ions
26H
2The concentration of O is 1.4mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.8mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.02A/cm
2, sedimentation time is 120s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 30min, obtains silicon thin film lithium ion battery negative electrode.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film, and the thickness of cobalt thin film is 1.2 μ m ± 0.1 μ m, and the thickness of silicon thin film is 300nm ± 50nm.Described cobalt thin film is a nano-cone array, and silicon thin film is an amorphous silicon membrane.
Embodiment 10
1) be supersound washing 10min in the watery hydrochloric acid of 0.5mol/L with copper base in concentration; Be neutral with distilled water flushing to copper base surface again, then with copper base supersound washing 10min in alcohol, vacuum drying; Copper base after obtaining cleaning, and it is simultaneously sticked insulating cement;
2) with cobalt nitrate, H
3BO
3After being dissolved in deionized water with ethylene diamine hydrochloride; Again through regulating pH to 4 with the watery hydrochloric acid of weight percentage 10% and the ammoniacal liquor of weight percentage 10%; Obtain containing the electrolyte 60ml of cobalt ions; Wherein, the concentration that contains cobalt nitrate in the electrolyte of cobalt ions is 1mol/L, contains H in the electrolyte of cobalt ions
3BO
3Concentration be 0.5mol/L, the concentration that contains ethylene diamine hydrochloride in the electrolyte of cobalt ions is 1.4mol/L;
This electrolyte that contains cobalt ions is placed 60 ℃ water-bath, and the copper base after will cleaning again places this electrolyte that contains cobalt ions, and at the copper base deposit cobalt film that powers on, the condition of electro-deposition cobalt thin film is: temperature is 60 ℃, and current density is 0.04A/cm
2, sedimentation time is 120s, obtains depositing the copper base of cobalt thin film;
3) place the magnetron sputtering chamber on the copper base of cobalt thin film depositing, adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 40sccm, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and the adjustment operating air pressure is 0.6Pa～0.7Pa, and sputtering time is 30min, obtains silicon thin film lithium ion battery negative electrode.
The silicon thin film lithium ion battery negative electrode of present embodiment preparation comprises copper base, is deposited on the cobalt thin film on the copper base and covers the silicon thin film on the cobalt thin film, and the thickness of cobalt thin film is 2.0 μ m ± 0.2 μ m, and the thickness of silicon thin film is 300nm ± 50nm.Described cobalt thin film is a nanometer mountain peak array, and silicon thin film is an amorphous silicon membrane.
Claims (10)
1. the preparation method of a silicon thin film lithium ion battery negative electrode may further comprise the steps:
1) substrate surface is cleaned the substrate after obtaining cleaning;
2) substrate after will cleaning places the electrolyte that contains cobalt ions, at the substrate deposit cobalt film that powers on;
3) obtain silicon thin film lithium ion battery negative electrode after adopting magnetron sputtering method depositing silicon film depositing on the substrate of cobalt thin film.
2. the preparation method of silicon thin film lithium ion battery negative electrode according to claim 1 is characterized in that, described substrate is a copper base.
3. the preparation method of silicon thin film lithium ion battery negative electrode according to claim 1; It is characterized in that; Substrate surface cleans and may further comprise the steps: is supersound washing 5min～10min in the diluted acid of 0.2mol/L～3mol/L with substrate in concentration, is neutral with distilled water flushing to substrate surface again, then with substrate supersound washing 5min～10min in alcohol; Vacuum drying, the substrate after obtaining cleaning.
4. the preparation method of silicon thin film lithium ion battery negative electrode according to claim 1; It is characterized in that; Step 2) in, the electrolyte that contains cobalt ions comprises the solubility cobalt salt, helps crystallizing agent, pH buffer and deionized water, and the described pH value that contains the electrolyte of cobalt ions is 2～6; Wherein, The concentration that contains solubility cobalt salt in the electrolyte of cobalt ions is 0.5mol/L～1.5mol/L, contains that to help the concentration of crystallizing agent in the electrolyte of cobalt ions be 0.2mol/L～2mol/L, and the concentration that contains pH buffer in the electrolyte of cobalt ions is 0.1mol/L～1mol/L.
5. the preparation method of silicon thin film lithium ion battery negative electrode according to claim 4 is characterized in that, described solubility cobalt salt is cobalt chloride or cobalt nitrate, and the described crystallizing agent that helps is an ethylene diamine hydrochloride, and described pH buffer is a boric acid.
6. the preparation method of silicon thin film lithium ion battery negative electrode according to claim 1 is characterized in that step 2) in, in the power on condition of deposit cobalt film of substrate be: temperature is 20 ℃～80 ℃, and current density is 0.008A/cm
2～0.06A/cm
2, sedimentation time is 120s～360s.
7. the preparation method of silicon thin film lithium ion battery negative electrode according to claim 1; It is characterized in that in the step 3), described magnetron sputtering method may further comprise the steps: the substrate that will deposit cobalt thin film places the magnetron sputtering chamber; Adopting the monocrystalline silicon target is the silicon source, is evacuated to 6 * 10
-3Below the Pa, feed argon gas, the gas flow of argon gas is 35sccm～45sccm, and the adjustment operating air pressure is 0.6Pa～O.7Pa, and bias voltage is-100V, and the target as sputter electric current is 0.04A, and sputtering time is 10min～60min.
8. the silicon thin film lithium ion battery negative electrode for preparing according to each described preparation method of claim 1～7.
9. silicon thin film lithium ion battery negative electrode according to claim 8; It is characterized in that; Comprise substrate, be deposited on on-chip cobalt thin film and cover the silicon thin film on the cobalt thin film, the thickness of described cobalt thin film is 500nm～3 μ m, and the thickness of described silicon thin film is 100nm～2 μ m.
10. silicon thin film lithium ion battery negative electrode according to claim 9 is characterized in that, described cobalt thin film is nano-cone array, nanometer mountain peak array, nanometer flower array or reticulated film, and described silicon thin film is an amorphous silicon membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101228938A CN102637852A (en) | 2012-04-24 | 2012-04-24 | Negative electrode of silicon film lithium ion battery and preparation method of negative electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101228938A CN102637852A (en) | 2012-04-24 | 2012-04-24 | Negative electrode of silicon film lithium ion battery and preparation method of negative electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102637852A true CN102637852A (en) | 2012-08-15 |
Family
ID=46622159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101228938A Pending CN102637852A (en) | 2012-04-24 | 2012-04-24 | Negative electrode of silicon film lithium ion battery and preparation method of negative electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102637852A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103268933A (en) * | 2013-05-06 | 2013-08-28 | 华南理工大学 | Al-Sn film negative electrode and preparation method thereof |
| CN110391469A (en) * | 2018-04-19 | 2019-10-29 | 北京金羽新能科技有限公司 | A kind of water system ion battery electrolyte |
| CN110993906A (en) * | 2019-11-21 | 2020-04-10 | 浙江大学 | Silicon-based lithium ion battery cathode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110189510A1 (en) * | 2010-01-29 | 2011-08-04 | Illuminex Corporation | Nano-Composite Anode for High Capacity Batteries and Methods of Forming Same |
-
2012
- 2012-04-24 CN CN2012101228938A patent/CN102637852A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110189510A1 (en) * | 2010-01-29 | 2011-08-04 | Illuminex Corporation | Nano-Composite Anode for High Capacity Batteries and Methods of Forming Same |
Non-Patent Citations (2)
| Title |
|---|
| 《Advanced Materials》 20101214 Zhang Shichao et al "Nickel Nanocone-Array Supported Silicon Anode for High-Performance Lithium Ion Batteries" 1-10 第22卷, 第47期 * |
| ZHANG SHICHAO ET AL: ""Nickel Nanocone-Array Supported Silicon Anode for High-Performance Lithium Ion Batteries"", 《ADVANCED MATERIALS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102891281B (en) * | 2012-10-18 | 2015-06-03 | 苏州晶纯新材料有限公司 | All solid-state thin film lithium ion battery cathode and preparation method thereof |
| CN103268933A (en) * | 2013-05-06 | 2013-08-28 | 华南理工大学 | Al-Sn film negative electrode and preparation method thereof |
| CN103268933B (en) * | 2013-05-06 | 2015-01-28 | 华南理工大学 | Al-Sn film negative electrode and preparation method thereof |
| CN110391469A (en) * | 2018-04-19 | 2019-10-29 | 北京金羽新能科技有限公司 | A kind of water system ion battery electrolyte |
| CN110993906A (en) * | 2019-11-21 | 2020-04-10 | 浙江大学 | Silicon-based lithium ion battery cathode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106654221B (en) | Three-dimensional porous carbon coating selenizing Zinc material and preparation method thereof for negative electrode of lithium ion battery | |
| Kim et al. | Electrochemical performances of Sn anode electrodeposited on porous Cu foam for Li-ion batteries | |
| CN107768720B (en) | Non-negative secondary lithium battery based on liquid electrolyte | |
| CN101667638B (en) | Preparation method of lithium silicon alloy membrane electrode used for lithium ion battery | |
| CN107732172B (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN109830646A (en) | A kind of composite metal negative pole and the battery comprising the cathode | |
| CN102544461A (en) | Anode material of lithium-ion battery and method for preparing anode material | |
| CN108258241A (en) | A kind of cathode of lithium battery for inhibiting lithium dendrite growth using ZIF-8 porous carbon materials | |
| CN113036153A (en) | Copper-based current collector for inducing preferential transverse deposition of lithium metal negative electrode and preparation method and application thereof | |
| CN112635698B (en) | Negative pole piece of zinc secondary battery and preparation method and application thereof | |
| CN103219503A (en) | Combined electrode material and preparation method thereof | |
| CN103996821A (en) | Negative film for lithium ion secondary battery as well as preparation method and application of negative film | |
| CN113937269A (en) | Three-dimensional porous copper current collector-lithium negative electrode integrated structure modified by silver particle coating and preparation method and application thereof | |
| CN101339989A (en) | Aluminum-tin alloy film for lithium ionic cell negative electrode and method for preparing the same | |
| CN102637852A (en) | Negative electrode of silicon film lithium ion battery and preparation method of negative electrode | |
| CN103400980A (en) | Iron sesquioxide/nickel oxide core-shell nanorod array film as well as preparation method and application thereof | |
| CN109473637B (en) | Protection method for long-cycle-life lithium negative electrode | |
| Huang et al. | Nickel/silicon core/shell nanosheet arrays as electrode materials for lithium ion batteries | |
| CN106601997B (en) | A kind of preparation method of the pulsed laser deposition fishing net shaped SiOx film on negative current collector material | |
| Wang et al. | Preparation and electrochemical performance of LiFePO4-based electrode using three-dimensional porous current collector | |
| CN111916671A (en) | Lithium ion battery cathode, lithium ion battery and preparation method of lithium ion battery cathode | |
| CN109825807B (en) | Gas phase synthesis method of thickness-controllable lithium metal negative electrode porous Zn current collector | |
| CN110931750A (en) | Copper-doped cobalt oxide porous nanosheet composite material and energy storage application | |
| CN108987673B (en) | Lithium negative electrode containing conductive protection film and preparation method and application thereof | |
| CN108899470A (en) | A kind of Li-S battery anode slice sandwich and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120815 |