CN109402567A - A kind of lithium ion battery silicon base alloy film and preparation method thereof - Google Patents
A kind of lithium ion battery silicon base alloy film and preparation method thereof Download PDFInfo
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- CN109402567A CN109402567A CN201811155923.9A CN201811155923A CN109402567A CN 109402567 A CN109402567 A CN 109402567A CN 201811155923 A CN201811155923 A CN 201811155923A CN 109402567 A CN109402567 A CN 109402567A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 63
- 239000010703 silicon Substances 0.000 title claims abstract description 63
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000000956 alloy Substances 0.000 title claims abstract description 48
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 47
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000004544 sputter deposition Methods 0.000 claims abstract description 73
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 239000011889 copper foil Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005030 aluminium foil Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 18
- 239000013077 target material Substances 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 37
- 238000012360 testing method Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000000151 deposition Methods 0.000 description 7
- 239000011856 silicon-based particle Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000004080 punching Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 238000005275 alloying Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3464—Sputtering using more than one target
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 methods of lithium ion battery silicon base alloy film, belong to technical field of lithium ion.Preparation method provided by the invention, comprising the following steps: under vacuum and inert gas conditions, open silicon target and metal targets, pre-sputtering is carried out to baffle；After pre-sputtering, substrate is sputtered, obtains lithium ion battery silicon base alloy film.The present invention uses pre-sputtering, can be avoided and target material surface partial oxide that may be present or pollutant are splashed on substrate, ensure that silicon-base alloy to the binding force and chemical property of substrate；Metal targets and silicon target sputter deposited on substrate simultaneously, ensure that the uniformity of silicon-base alloy film, can alleviate the bulk effect of silicon.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of lithium ion battery silicon base alloy film and its systems
Preparation Method.
Background technique
Lithium ion battery because its light-weight, small in size, specific energy and it is highly-safe the advantages that, be widely used in energy storage,
The fields such as space flight, traffic power, 3C, wherein energy density is the important consideration factor of lithium ion battery applications, high-energy density
It is one of the important way for improving lithium ion battery cruising ability.
Silica-base material is widely used in the negative electrode material of lithium ion secondary battery, including Si-C composite material, the sub- silicon of oxidation
Composite material and silicon-base alloy material, silica-base material because bulk effect huge during removal lithium embedded limit its lithium from
Application in sub- battery brings inconvenience to the application of silica-base material in actual production, therefore how to solve silica-base material
Bulk effect is current urgent problem to be solved.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of lithium ion battery silicon base alloy film and preparation method thereof,
Adopt that the silicon-base alloy film volumetric effect being obtained by the present invention is small, expand silicon-base alloy thin-film material applies model
It encloses.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of lithium ion battery silicon base alloy film, comprising the following steps:
Under vacuum and inert gas conditions, silicon target and metal targets are opened, pre-sputtering is carried out to baffle；Pre-sputtering knot
Shu Hou sputters substrate, obtains lithium ion battery silicon base alloy film.
Preferably, the material of the metal targets includes aluminium, copper, nickel or zinc.
Preferably, the substrate includes copper foil, aluminium foil, foam copper or nickel foam.
Preferably, when pre-sputtering, the sputtering power of the silicon target is 50~1000W, the sputtering function of the metal targets
Rate is 20~150W.
Preferably, the time of the pre-sputtering is 1~30min.
Preferably, when sputtering, the sputtering power of the silicon target is 1000~3000W, the sputtering function of the metal targets
Rate is 100~1000W.
Preferably, the time of the sputtering is 60~200min.
Preferably, the pre-sputtering and the bias-voltage of sputtering independently are 50~600V.
Preferably, the pre-sputtering and the temperature of sputtering are 80~200 DEG C.
The present invention also provides the lithium ion battery silicon base alloy films that preparation method described in above-mentioned technical proposal obtains.
The present invention provides a kind of preparation methods of lithium ion battery silicon base alloy film, comprising the following steps: in vacuum
Under inert gas conditions, silicon target and metal targets are opened, pre-sputtering is carried out to baffle；After pre-sputtering, to substrate into
Row sputtering, obtains lithium ion battery silicon base alloy film material.The present invention carries out pre-sputtering to baffle, can be avoided target table
Face partial oxide that may be present or pollutant are splashed on substrate, ensure that silicon-base alloy film to the binding force of substrate and
Chemical property；Metal targets and silicon target sputter deposited on substrate simultaneously, can generate gap, Neng Gouhuan between two kinds of particles
Solve the bulk effect of silicon.From embodiment it can be seen that the full electric rebound rate of silicon-base alloy film provided by the invention be 50.9~
83.0%, 100 weeks circulation rebound rates are 12.0~26.4%, and it is excellent steady to illustrate that silicon-base alloy film provided by the invention has
Qualitative and cyclical stability.
Further, porous or coarse substrate enhances the binding force between substrate and deposited particles, inhibits alloy film
Demi-inflation effect；In addition to this, the power by control silicon target and metal targets is different, make silicon particle and metallic with
On different deposition rates to substrate, it ensure that silicon particle and metallic are uniformly deposited on substrate, it is ensured that silicon particle
With the deposition efficiency of metallic, the performance of silicon-base alloy film is improved.
Detailed description of the invention
Fig. 1 is the loop test effect picture of the button electrical testing of the silicon-base alloy film of Examples 1 to 3 preparation.
Specific embodiment
The present invention provides a kind of preparation methods of lithium ion battery silicon base alloy film, comprising the following steps:
Under vacuum and inert gas conditions, silicon target and metal targets are opened, pre-sputtering is carried out to baffle；Pre-sputtering knot
Shu Hou sputters substrate, obtains lithium ion battery silicon base alloy film.
The present invention opens silicon target and metal targets under vacuum and inert gas conditions, carries out pre-sputtering to baffle.
In the present invention, the vacuum degree of the pre-sputtering is preferably 9.9 × 10-1~9 × 100Pa.In the present invention, described
The vacuum degree of pre-sputtering preferably passes through following steps and controls to obtain: system being first evacuated to 9.9 × 10-1~9 × 100Pa；It opens
Dynamic molecular pump, makes system vacuum degree < 9.0 × 10-4Pa；Open air valve, be passed through inert gas, make the vacuum degree 9.9 of system ×
10-1~9 × 100Pa.In the present invention, the inert gas preferably includes argon gas or helium.
In the present invention, when pre-sputtering, the sputtering power of the silicon target is preferably 50~1000W, more preferably 200~
800W, most preferably 400~600W.In the present invention, when pre-sputtering, the sputtering power of the metal targets is preferably 20~
150W, more preferably 30~130W, most preferably 50~100W.In the present invention, the bias-voltage of the pre-sputtering is preferably 50
~600V, more preferably 100~550V, most preferably 150~500V.In the present invention, the temperature of the pre-sputtering is preferably
80~200 DEG C, more preferably 100~180 DEG C are most preferably 120~160 DEG C.In the present invention, the time of the pre-sputtering
Preferably 1~30min, more preferably 5~25min, most preferably 10~20min.
In the present invention, the concrete operation step of the pre-sputtering are as follows: silicon target and metal targets line and substrate it
Between baffle is set, carry out pre-sputtering；Due to the presence of baffle, it is splashed to silicon particle and metallic on baffle.In the present invention
In, the purpose of pre-sputtering is to avoid partial oxide that may be present in silicon target and metal targets or pollutant being splashed to base
On piece ensure that the binding force and chemical property of subsequent silicon-base alloy film and substrate.
In the present invention, the material of the metal targets preferably includes aluminium, copper, nickel or zinc.
The present invention does not have special restriction to the material of the baffle, using baffle material well known to those skilled in the art
, specifically, such as stainless steel material.
After pre-sputtering, the present invention sputters substrate, obtains lithium ion battery silicon base alloy film material.
When sputtering, the present invention does not have special requirement, those skilled in the art to the power of the silicon target and metal targets
The capacity of the lithium ion battery of member according to actual needs is selected；In the present invention, the sputtering power of the silicon target
Preferably 1000~3000W, the sputtering power of the metal targets are preferably 100~1000W.In the present invention, the sputtering
Bias-voltage be preferably 50~600V, more preferably 100~550V, most preferably 150~500V.In the present invention, described to splash
The temperature penetrated is preferably 80~200 DEG C, more preferably 100~180 DEG C, most preferably 120~160 DEG C.In the present invention, described
The time of sputtering is preferably 60~200min, more preferably 120~180min, most preferably 100~160min.In the present invention
In, the vacuum degree of the sputtering is preferably 9.9 × 10-1~9 × 100Pa。
In the present invention, the material of the substrate preferably includes copper foil, aluminium foil, foam copper or nickel foam, more preferably copper
Foil.In the present invention, the copper foil preferably includes to stretch copper foil, rolled copper foil, electrochemical deposition copper foil or punching copper foil.At this
In invention, porous or coarse substrate enhances the binding force between substrate and deposited particles, it is suppressed that the expansion of alloy membrane part silicon
Effect.
In the present invention, the substrate preferably carries out sputtering sedimentation in rotary manner.In the present invention, the substrate
Revolving speed is preferably 5~30r/min, more preferably 10~25r/min, most preferably 15~20r/min.The rotation of substrate in the present invention
Turn, can guarantee for silicon target and metal targets uniform particle to be deposited on substrate, improves the uniformity of silicon-base alloy film,
Further alleviate the bulk effect of silicon-base alloy film.
After sputtering, the present invention preferably is off shielding power supply, after cooling down, closes inert gas air valve.In the present invention
In, the cooling is preferably cooled to 10~50 DEG C.
In the present invention, metal targets and silicon target sputter deposited on substrate simultaneously, ensure that the equal of silicon-base alloy film
Even property achievees the purpose that alleviate silicon-base alloy film volumetric effect.
Further, different with the power of metal targets by control silicon target, make silicon particle and metallic with difference
Scale deposits to substrate on, ensure that silicon particle and metallic are uniformly deposited on substrate, it is ensured that silicon particle and gold
The deposition efficiency for belonging to particle, improves the performance of silicon-base alloy film.
The present invention also provides the lithium ion battery silicon base alloy films that preparation method described in above-mentioned technical proposal obtains.?
In the present invention, the bulk effect of the lithium ion battery silicon base alloy film is in charge and discharge process, and the insertion of lithium ion is deviate from
With apparent volume expansion shrinkage phenomenon, this is caused by the embedding lithium mechanism of silica-base material alloying, and volume expansion generally exists
300% or more.Two kinds of particle co-depositions are had gap by way of cosputtering by the present invention between matrix surface, particle, empty
Gap can alleviate certain volume expansion；Matrix surface can pass through roughening treatment, enhance the combination between matrix and active material
Power inhibits part bulking effect；In sputtering process, base station at the uniform velocity rotates, and particle deposition is uniform, alleviates bulking effect.Embodiment
As can be seen that under suitable process conditions, 100 weeks circulation volume conservation rates about 85% of sample.
Lithium ion battery silicon base alloy film provided by the invention and preparation method thereof is carried out below with reference to embodiment detailed
Thin explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Using silicon target and aluminium target as sputtering target material, copper foil is stretched as substrate；
System is vacuumized, is 9.0 × 10 to system pressure0When Pa；Molecular pump is opened, when system pressure reaches
9.0×10-4Pa opens substrate rotation；When system is heated to 140 DEG C；It is passed through Ar gas, adjusting chamber pressure is 1.0 × 100Pa
When, grid bias power supply is opened, adjusts voltage to 600V, butterfly is between substrate and silicon target and metal targets line；It opens
Pre-sputtering, pre-sputtering time 10min, the power of the silicon target are 300W, and the power of aluminium target is 80W；After pre-sputtering,
Bias mains voltage is adjusted to 100V, baffle is opened, adjusts chamber pressure to 4.0 × 10-1Pa, adjust the power of silicon target to
2500W, the power of aluminium target sputter 120min to 350W；Two targets are closed after sputtering, are reduced temperature to 30 DEG C, are closed
Air valve, pass hull closure；Lithium ion battery silicon base alloy film is obtained, sample 1 is denoted as.
Button electrical testing is done into lithium ion battery silicon base alloy film cut-parts, the full electricity rebound and circulation that button electrical testing obtains are anti-
It plays data and is shown in Table 1；Loop test effect is as shown in Figure 1.
Embodiment 2
Using silicon target and aluminium target as sputtering target material, for punching copper foil as substrate, the punching copper foil is with porous
Copper foil；
System is vacuumized, is 9.0 × 10 to system pressure0When Pa；Molecular pump is opened, when system pressure reaches
9.0×10-4Pa opens substrate rotation；When system is heated to 140 DEG C；It is passed through Ar gas, adjusting chamber pressure is 1.0 × 100Pa
When, grid bias power supply is opened, adjusts voltage to 600V, butterfly is between substrate and silicon target and metal targets line；It opens
Pre-sputtering, pre-sputtering time 10min, the power of the silicon target are 300W, and the power of aluminium target is 80W；Pre-sputtering terminates, and adjusts
Bias mains voltage is saved to 100V, baffle is opened afterwards, adjusts chamber pressure to 4.0 × 10-1Pa, adjust the power of silicon target to
2500W, the power of aluminium target sputter 120min to 350W；Two targets are closed after sputtering, are reduced temperature to 30 DEG C, are closed
Air valve, pass hull closure；Lithium ion battery silicon base alloy film is obtained, sample 2 is denoted as.
Button electrical testing is done into lithium ion battery silicon base alloy film cut-parts, button electrical testing obtains full electricity rebound and circulation rebound
Data are shown in Table 1；Loop test effect is as shown in Figure 1.
Embodiment 3
Using silicon target and aluminium target as sputtering target material, for punching copper foil as substrate, the punching copper foil is with porous
Copper foil；
System is vacuumized, is 9.0 × 10 to system pressure0When Pa；Molecular pump is opened, when system pressure reaches
9.0×10-4Pa opens substrate rotation；When system is heated to 140 DEG C；It is passed through Ar gas, adjusting chamber pressure is 1.0 × 100Pa
When, grid bias power supply is opened, adjusts voltage to 600V, butterfly is between substrate and silicon target and metal targets line；It opens
Pre-sputtering, pre-sputtering time 10min, the power of the silicon target are 300W, and the power of aluminium target is 80W；After pre-sputtering,
Bias mains voltage is adjusted to 100V, baffle is opened, adjusts chamber pressure to 4.0 × 10-1Pa, adjust the power of silicon target to
2500W, the power of aluminium target sputter 150min to 350W；Two targets are closed after sputtering, are reduced temperature to 30 DEG C, are closed
Air valve, pass hull closure；Lithium ion battery silicon base alloy film is obtained, sample 3 is denoted as.
Button electrical testing is done to lithium ion battery silicon base alloy film cut-parts, button electrical testing obtains full electricity rebound and circulation rebound
Data are shown in Table 1；Loop test effect is as shown in Figure 1.
1 Examples 1 to 3 of table obtains the full electricity rebound and circulation rebound data that silicon-base alloy film buckles electrical testing
As it can be seen from table 1 silicon-base alloy film prepared by the present invention has excellent stability and cyclical stability.
Two kinds of particle co-depositions are had gap, gap by way of cosputtering by the present invention between matrix surface, particle
Certain volume expansion can be alleviated；Matrix surface can pass through roughening treatment, enhance the binding force between matrix and active material,
Inhibit part bulking effect；In sputtering process, base station at the uniform velocity rotates, and particle deposition is uniform, alleviates bulking effect.Embodiment can be with
Find out, it is 12.0 that the full electric rebound rate of silicon-base alloy film provided by the invention, which is 50.9~83.0%, 100 weeks circulation rebound rates,
~26.4%；Illustrate that silicon-base alloy film provided by the invention has excellent stability and cyclical stability.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium ion battery silicon base alloy film, comprising the following steps:
Under vacuum and inert gas conditions, silicon target and metal targets are opened, pre-sputtering is carried out to baffle；Pre-sputtering terminates
Afterwards, substrate is sputtered, obtains lithium ion battery silicon base alloy film.
2. preparation method according to claim 1, which is characterized in that the material of the metal targets include aluminium, copper, nickel or
Zinc.
3. preparation method according to claim 1 or 2, which is characterized in that the substrate includes copper foil, aluminium foil, foam copper
Or nickel foam.
4. preparation method according to claim 1, which is characterized in that when pre-sputtering, the sputtering power of the silicon target is
50~1000W, the sputtering power of the metal targets are 20~150W.
5. preparation method according to claim 1 or 4, which is characterized in that the time of the pre-sputtering is 1~30min.
6. preparation method according to claim 1, which is characterized in that when sputtering, the sputtering power of the silicon target is
1000~3000W, the sputtering power of the metal targets are 100~1000W.
7. preparation method according to claim 1 or 6, which is characterized in that the time of the sputtering is 60~200min.
8. preparation method according to claim 1, which is characterized in that the pre-sputtering and the bias-voltage of sputtering independently are
50~600V.
9. preparation method according to claim 1, which is characterized in that the pre-sputtering and the temperature of sputtering are 80~200
℃。
10. the lithium ion battery silicon base alloy film that any one of claim 1~9 preparation method obtains.
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| CN201811155923.9A CN109402567A (en) | 2018-09-30 | 2018-09-30 | A kind of lithium ion battery silicon base alloy film and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111584828A (en) * | 2020-04-28 | 2020-08-25 | 江西昌大高新能源材料技术有限公司 | Silicon/metal composite film cathode structure of lithium ion battery and preparation method thereof |
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