CN109698312A - A kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery - Google Patents
A kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery Download PDFInfo
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- CN109698312A CN109698312A CN201811487505.XA CN201811487505A CN109698312A CN 109698312 A CN109698312 A CN 109698312A CN 201811487505 A CN201811487505 A CN 201811487505A CN 109698312 A CN109698312 A CN 109698312A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
- 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 present invention provides a kind of preparation method of first crystalline state nano-silicon negative electrode material for lithium battery, the following steps are included: choosing conductive film material, cut according to the carrier size of plasma enhanced chemical vapor deposition (PECVD) equipment used as substrate material；The cleaning of hydrogen plasma bombardment is carried out to substrate；The process gas such as hydrogen, silane are passed through, suitable deposition process conditions are set, the first crystalline state nano-silicon negative electrode material of deposition preparation 200~1000nm thickness on copper foil substrate.Provided by the present invention for the first crystalline state nano-silicon negative electrode material and preparation method thereof of lithium battery, the PECVD device generallyd use using photovoltaic industry, the thickness uniformity of first crystalline state nano silicon material of preparation and good with the adhesion of substrate, negative electrode material as lithium battery, compared with traditional graphite cathode material, the electrical performance indexes such as the specific discharge capacity of lithium cell negative pole can be increased substantially.
Description
Technical field
The present invention relates to field of material engineering technology, in particular to utilize plasma enhanced chemical vapor deposition
(PECVD) technology preparation can be used for the method for the first crystalline state nano silicon material of cathode of lithium battery.
Background technique
Currently commercially common lithium ion battery negative material is the graphite of various forms, theoretical capacity 372mAh/
G is the 1/10 of lithium metal theoretical discharge capacity.The major advantage of graphite is insertion and the abjection good reversibility of lithium, cycle performance
It is excellent, it can satisfy many practical application needs.But the disadvantage is that capacity density is too small, it can not meet lithium ion battery large capacity and deposit
The demand for development of storage, high current or high power discharge.Other than carbon, many simple substance such as: Sn, Sb, Si can be closed with lithiumation
Alloy is formed using the negative electrode material as lithium ion battery.Wherein Si either specific discharge capacity or volume and capacity ratio be all very
Height, specific discharge capacity have reached 4200mAh/g, are 10 times to the greatest extent of carbon.Si has the suction lithium electricity close to carbon material simultaneously
Position, therefore, it has become a mains direction of studying of next-generation lithium ion battery negative material.
Traditional silica-base film material can be divided into crystal silicon thin film and amorphous silicon membrane two major classes.Crystalline silicon is due to its knot
The periodically ordered arrangement of structure, when being used as cathode of lithium battery, with the insertion and abjection of lithium ion, the volume change of silicon substrate
It is very big.Silicon volume change before and after being embedded in lithium reaches 300%, and (electric discharge refers to the insertion of lithium, leads to silicon volume expansion；Charging refers to lithium
Abjection, lead to the contraction of silicon substrate).Huge volume change results in electrode and loses contact, increases electrochemical impedance.Cause
This, improves key of the silicon as negative electrode material cycle performance, and volume drastic change is to electrode itself after being lithium insertion to be overcome and deviating from
Bring stress impact.Amorphous silicon membrane have unlike crystalline material long-range order its with shortrange order, the small ruler in part
Very little silicon atom lattice arrangement just constitutes small crystal grain.The included fault of construction of amorphous silicon material, comprising: dangling bonds, weak
Key, vacancy and micropore provide certain freedom degree to volume expansion and stress release.
When the size of the tiny crystal grains in amorphous silicon material is in nanoscale, which is referred to as just crystalline state nano-silicon material
Material.First crystalline state nano silicon material has both the advantage of crystalline silicon material and amorphous silicon material, nano-scale as cathode of lithium battery
Crystal grain ensure that material reversible capacity characteristic with higher；Simultaneously because its internal fault of construction, allows to more brilliant
Body silicon materials can bear bigger volume change impact, and integrated stress more balances, and have more longlasting cycle life.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of first crystalline state nano-silicon negative electrode material for lithium battery, with
Improve the electrical properties such as the specific discharge capacity of lithium cell negative pole material.
In order to solve the problems, such as that conventional graphite negative material specific capacity is insufficient, the technical scheme is that providing one kind
The preparation method of first crystalline state nano-silicon negative electrode material for lithium battery, comprising the following steps: step 1 chooses conductive thin membrane material
Expect and is cut by equipment carrier size；Step 2, fixed by substrate material and PECVD device carrier and load facility is evacuated；
Step 3 is passed through hydrogen and carries out Bombardment and cleaning to substrate surface with the plasma generated；Step 4 is proportionally passed through hydrogen
The process gas such as gas, silane simultaneously keep setting pressure to stablize；Step 5 is sunk according to technological parameters such as temperature, the radio-frequency powers of setting
The first crystalline state nano silicon material of product.
Further, conductive film material can be the metal materials such as copper foil, aluminium foil in step 1, be also possible to conduction
Composite material.
Further, use in step 2 with plasma enhanced chemical vapor deposition (PECVD) equipment, it is heavy to have
The fixing means of the features such as product speed is fast, technological temperature is low, substrate material and equipment carrier can be pressed using mechanical periphery
Plate is fixed, and can also be fixed using attaching.
Further, in step 3 using hydrogen plasma to the Bombardment and cleaning of substrate, technological parameter includes: RF frequency
13.56MHz, 20~50W of radio-frequency power, 50~100Pa of Hydrogen Vapor Pressure, 100~200 DEG C of underlayer temperature, the Ion Cleaning time 1~
5 minutes.
Further, in step 4, being passed through the process gas such as hydrogen, silane by a certain percentage, (hydrogen/silane ratio is 10
~30), the source as essential element in first crystalline state nano silicon material, can also be added the impurity gas such as phosphine, borine, to improve
The chemical property of material.Range: 100~200Pa is arranged in gas pressure, and pressure is kept for 1 minute or more time after stablizing, to protect
It is uniform to demonstrate,prove process gas mix.
Further, in steps of 5, the technological parameter of setting includes: RF frequency 13.56MHz, 20~50W of radio-frequency power,
100~200 DEG C of underlayer temperature.The first crystalline state nano silicon material as lithium cell negative pole can be completed using fixed technological parameter
Preparation, can also combine different technological parameters (including: gas component, air pressure, power, temperature etc.), prepare nano-silicon
Composite film material, 200~1000nm of thickness.
The present invention provides a kind of preparation method of first crystalline state nano-silicon negative electrode material for lithium battery, using plasma
Enhance the deposition preparation of chemical vapor deposition (PECVD) equipment, the first crystalline state nano silicon material and substrate adhesion of preparation are good, thick
Degree control is uniform, and depositional mode is simple, stable process conditions.This method preparation first crystalline state nano silicon material, for containing
The amorphous silicon structure of nano-scale tiny crystal grains.First crystalline state nano silicon material has both crystalline silicon material as cathode of lithium battery
With the advantage of amorphous silicon material, when nano-sized grains ensure that silicon and lithium ion form alloy, the material is with higher
Reversible capacity characteristic；Simultaneously because its internal fault of construction, allows to that bigger volume can be born compared with crystalline silicon material
Variation impact, integrated stress more balance, and have more longlasting cycle life.
Detailed description of the invention
Invention is described further with reference to the accompanying drawing:
Fig. 1 provides a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery for the embodiment of the present invention
Flow chart of steps；
Fig. 2 is the 8 microns thick copper foil substrate photo cut, having a size of 10cm*10cm；
Fig. 3 is 8 microns thick copper foil substrate surface SEM picture；
Fig. 4 is the sample photo of the first crystalline state nano silicon material of deposition 200nm thickness on copper foil substrate；
Fig. 5 a is 200nm thickness just crystalline state 50 microns of range SEM pictures of nano silicon material；
Fig. 5 b is 200nm thickness just crystalline state 10 microns of range SEM pictures of nano silicon material；
Fig. 6 is the charge-discharge performance test of the first crystalline state nano silicon material of 200nm thickness；
Fig. 7 is the sample photo of the first crystalline state nano silicon material of deposition 1000nm thickness on copper foil substrate；
Fig. 8 a is 1000nm thickness just crystalline state 50 microns of range SEM pictures of nano silicon material；
Fig. 8 b is 1000nm thickness just crystalline state 10 microns of range SEM pictures of nano silicon material；
Fig. 9 is the just crystalline state nano silicon material charge-discharge performance test of 1000nm thickness.
Specific embodiment
A kind of first crystalline state nano-silicon cathode for lithium battery is proposed to the present invention below in conjunction with the drawings and specific embodiments
The preparation method of material is described in further detail.According to following explanation and claims, advantages and features of the invention will
It becomes apparent from.It should be noted that attached drawing is all made of very simplified form and using non-accurate ratio, only to convenient, bright
The purpose of the embodiment of the present invention is aided in illustrating clearly.
Core of the invention thought is, the present invention provides a kind of first crystalline state nano-silicon negative electrode material for lithium battery
Preparation method, using plasma enhance the deposition preparation of chemical vapor deposition (PECVD) equipment, the nano silicon material and lining of preparation
Bottom adhesion is good, the thickness uniformity, and depositional mode is simple, stable process conditions.The first crystalline state nanometer of this method preparation
Silicon materials, micro-structure are the amorphous non crystalline structure containing nano-sized grains.Nanocrystal ensure that silicon is formed with lithium ion
When alloy, specific discharge capacity and volume and capacity ratio with higher.The included fault of construction of amorphous silicon material, comprising: dangling bonds,
Weak bond, vacancy and micropore provide certain freedom degree to volume expansion and stress release, can bear more compared with crystalline silicon material
Big volume change impact, integrated stress more balance.Therefore this just crystalline state nano silicon material is being kept as lithium cell negative pole
It, will be with more longlasting cycle life while high reversible capacity characteristic.
Fig. 1 provides a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery for the embodiment of the present invention
Flow chart of steps.Referring to Fig.1, a kind of preparation method of first crystalline state nano-silicon negative electrode material for lithium battery is provided, including with
Lower step:
S11, conductive film material is chosen, cut by carrier size making substrate material；
S12, substrate material and PECVD device carrier are fixed；
S13, Bombardment and cleaning is carried out to substrate surface using hydrogen plasma；
S14, the process gas such as hydrogen, silane are passed through, and setting pressure is kept to stablize；
S15, just crystalline state nano silicon material is deposited according to technological parameters such as temperature, the radio-frequency powers of setting.
Specifically, in S11, select conductive film material as substrate, conductive film material can be copper foil, aluminium foil etc.
Metal material is also possible to conducing composite material.Substrate material is cut according to the requirement of PECVD device carrier.
In S12, substrate material and equipment carrier are fixed, the fixing means of substrate material and equipment carrier can be with
It is fixed using mechanical periphery pressing plate, is also possible to attach and fix, the carrier with substrate is packed into PECVD device.
In S13, cleaning of the using plasma to substrate first vacuumizes PECVD device, when vacuum degree is 10-4Pa
When above, heater is opened, purge gas is then passed to, keep certain air pressure, opened radio-frequency power supply and switch starter, with generation
Plasma bombardment substrate material surface.Technological parameter includes: RF frequency 13.56MHz, 20~50W of radio-frequency power, air pressure 50
~100Pa, 100~200 DEG C of underlayer temperature.Gas can choose the common purge gas such as hydrogen, argon gas, and scavenging period 1~
5min。
In S14, it is passed through the process gas such as hydrogen, silane (hydrogen/silane ratio is 10~30) by a certain percentage, as first
The source of essential element in crystalline state nano silicon material, can also be added the impurity gas such as phosphine, borine, to improve the electrochemistry of material
Performance.Range: 100~200Pa is arranged in gas pressure, and pressure is kept for 1 minute or more time after stablizing, to guarantee that process gas is mixed
It closes uniform.
In S15, the technological parameter of setting includes: RF frequency 13.56MHz, 20~50W of radio-frequency power, underlayer temperature 100
~200 DEG C.The preparation of the first crystalline state nano silicon material as lithium cell negative pole can be completed using fixed technological parameter, it can also be with
Different technological parameters (including: gas component, air pressure, power, temperature etc.) is combined, the THIN COMPOSITE membrane material of nano-silicon is prepared
Material, 200~1000nm of thickness.
Embodiment one
A kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery includes:
(1) 8 microns of thick copper foils are chosen as substrate, by carrier having a size of cutting 10cm*10cm；
(2) copper foil substrate and equipment carrier are fixed, by the way of the press strip of both sides, tighten fixed screw, by band
There is the carrier of substrate to be packed into PECVD device；
(3) PECVD device is vacuumized, when vacuum degree is 10-4When Pa or more, heater, heter temperature 500 are opened
DEG C, measure 180 DEG C of underlayer temperature.Hydrogen is passed through as purge gas, keeps certain air pressure, air pressure 50Pa opens radio frequency electrical
Source switch, RF frequency 13.56MHz, radio-frequency power 20W bombard substrate material surface, scavenging period with the hydrogen plasma of generation
2min。
(4) it is passed through the process gas such as hydrogen, silane, H by a certain percentage2/SiH4=10, range is arranged in gas pressure:
100Pa, pressure is kept for 1 minute or more time after stablizing, to guarantee that process gas mix is uniform.
(5) it opens radio-frequency power supply and switchs starter, nano silicon material, the technological parameter of setting are deposited on processed substrate
It include: RF frequency 13.56MHz, radio-frequency power 30W, 180 DEG C of underlayer temperature, sedimentation time 30min, first crystalline state nano silicon material
Thickness 200nm.
Fig. 2 is cut good 8 microns thick copper foil substrate photo used in embodiment one, having a size of 10cm*10cm；
Fig. 3 is in embodiment one using 8 microns thick copper foil substrate surface SEM picture；Fig. 4 is on the copper foil substrate prepared in embodiment one
The sample photo for depositing the first crystalline state nano silicon material of 200nm thickness, has been cut into disk；Fig. 5 a is 200nm thickness just crystalline state
50 microns of range SEM pictures of nano silicon material；Fig. 5 a is 200nm thickness just crystalline state 10 microns of range SEM pictures of nano silicon material；
Fig. 6 is the charge-discharge performance test of the first crystalline state nano silicon material of 200nm thickness.
Embodiment two
A kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery includes:
(1) 8 microns of thick copper foils are chosen as substrate, by carrier having a size of cutting 10cm*10cm；
(2) copper foil substrate and equipment carrier are fixed, by the way of the press strip of both sides, tighten fixed screw, by band
There is the carrier of substrate to be packed into PECVD device；
(3) PECVD device is vacuumized, when vacuum degree is 10-4When Pa or more, heater, heter temperature 500 are opened
DEG C, measure 180 DEG C of underlayer temperature.Hydrogen is passed through as purge gas, keeps certain air pressure, air pressure 50Pa opens radio frequency electrical
Source switch, RF frequency 13.56MHz, radio-frequency power 30W bombard substrate material surface, scavenging period with the hydrogen plasma of generation
1min。
(4) it is passed through the process gas such as hydrogen, silane, H by a certain percentage2/SiH4=20, range is arranged in gas pressure:
100Pa, pressure is kept for 1 minute or more time after stablizing, to guarantee that process gas mix is uniform.
(5) it opens radio-frequency power supply and switchs starter, nano silicon material, the technological parameter of setting are deposited on processed substrate
It include: RF frequency 13.56MHz, radio-frequency power 30W, 180 DEG C of underlayer temperature, sedimentation time 150min, first crystalline state nano silicon material
Thickness 1000nm.
Fig. 2 is cut good 8 microns thick copper foil substrate photo used in embodiment two, having a size of 10cm*10cm；
Fig. 3 is in embodiment two using 8 microns thick copper foil substrate surface SEM picture；Fig. 7 is on the copper foil substrate prepared in embodiment two
The sample photo for depositing the first crystalline state nano silicon material of 1000nm thickness, has been cut into disk；Fig. 8 a is 1000nm thickness primary crystal
50 microns of range SEM pictures of state nano silicon material；Fig. 8 b is 1000nm thickness just 10 microns of range SEM figures of crystalline state nano silicon material
Piece；Fig. 9 is the just crystalline state nano silicon material charge-discharge performance test of 1000nm thickness.
Obviously, those skilled in the art can carry out various changes and deformation without departing from essence of the invention to the present invention
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (7)
1. a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery, which comprises the following steps:
Step 1 is chosen conductive film material and is cut by equipment carrier size；
Step 2, fixed by substrate material and PECVD device carrier and load facility is evacuated；
Step 3 is passed through hydrogen and carries out Bombardment and cleaning to substrate surface with the plasma generated；
Step 4 is proportionally passed through the process gas such as hydrogen, silane and setting pressure is kept to stablize；
Step 5 deposits just crystalline state nano silicon material according to the temperature of setting, radio-frequency power technological parameter.
2. a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery as described in claim 1, feature
It is, conductive film material can be copper foil, aluminium foil or conducing composite material in step 1.
3. a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery as described in claim 1, feature
Be, use in step 2 with plasma enhanced chemical vapor deposition PECVD device, have that deposition velocity is fast, process warm
The features such as low is spent, the fixing means of substrate material and equipment carrier can be fixed using mechanical periphery pressing plate, can also be adopted
It is fixed with attaching.
4. a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery as described in claim 1, feature
It is, in step 3 using hydrogen plasma to the Bombardment and cleaning of substrate, technological parameter includes: RF frequency 13.56MHz, radio frequency
20~50W of power, 50~100Pa of Hydrogen Vapor Pressure, 100~200 DEG C of underlayer temperature, the Ion Cleaning time 1~5 minute.
5. a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery as described in claim 1, feature
It is, in step 4, is passed through hydrogen, silane process gas by a certain percentage, hydrogen/silane ratio is 10~30, as first crystalline state
Phosphine, borane doping gas can also be added, gas pressure setting range in the source of essential element in nano silicon material: 100~
200Pa, pressure is kept for 1 minute or more time after stablizing, to guarantee that process gas mix is uniform.
6. a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery as described in claim 1, in step 5
In, the technological parameter of setting includes: RF frequency 13.56MHz, 20~50W of radio-frequency power, and 100~200 DEG C of underlayer temperature.
7. a kind of preparation method of the first crystalline state nano-silicon negative electrode material for lithium battery as described in claim 1, in step 5
In, the preparation of the first crystalline state nano silicon material as lithium cell negative pole is completed using fixed technological parameter or joins different technique
Number, comprising: gas component, air pressure, power, temperature combination prepare the composite film material of nano-silicon, 200~1000nm of thickness.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115348949A (en) * | 2020-04-03 | 2022-11-15 | 韩国金属硅股份公司 | Method for manufacturing amorphous silicon composite and apparatus for manufacturing amorphous silicon composite |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075173A (en) * | 1992-12-28 | 1993-08-11 | 北京航空航天大学 | A kind of preparation method of Nano thin film |
| CN103474632A (en) * | 2012-06-07 | 2013-12-25 | 中国科学院物理研究所 | Negative electrode material used for lithium battery and preparation method and application thereof |
| TWI584519B (en) * | 2015-05-29 | 2017-05-21 | 國立東華大學 | Lithium ion battery, and composite electrode material and fabrication method thereof |
| CN107667186A (en) * | 2015-04-07 | 2018-02-06 | 荷兰能源研究中心基金会 | Rechargeable battery and its manufacture method |
-
2018
- 2018-12-06 CN CN201811487505.XA patent/CN109698312A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075173A (en) * | 1992-12-28 | 1993-08-11 | 北京航空航天大学 | A kind of preparation method of Nano thin film |
| CN103474632A (en) * | 2012-06-07 | 2013-12-25 | 中国科学院物理研究所 | Negative electrode material used for lithium battery and preparation method and application thereof |
| CN107667186A (en) * | 2015-04-07 | 2018-02-06 | 荷兰能源研究中心基金会 | Rechargeable battery and its manufacture method |
| TWI584519B (en) * | 2015-05-29 | 2017-05-21 | 國立東華大學 | Lithium ion battery, and composite electrode material and fabrication method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MICHAEL W. FORNEY ET AL.: "High performance silicon free-standing anodes fabricated by low-pressure and plasma-enhanced chemical vapor deposition onto carbon nanotube electrodes", 《JOURNAL OF POWER SOURCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115348949A (en) * | 2020-04-03 | 2022-11-15 | 韩国金属硅股份公司 | Method for manufacturing amorphous silicon composite and apparatus for manufacturing amorphous silicon composite |
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Application publication date: 20190430 |