CN106450488A - In-situ preparation method of lithium-sulfur battery based on silicon cathode - Google Patents
In-situ preparation method of lithium-sulfur battery based on silicon cathode Download PDFInfo
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- CN106450488A CN106450488A CN201611165018.2A CN201611165018A CN106450488A CN 106450488 A CN106450488 A CN 106450488A CN 201611165018 A CN201611165018 A CN 201611165018A CN 106450488 A CN106450488 A CN 106450488A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 64
- 239000010703 silicon Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 128
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 115
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000003860 storage Methods 0.000 claims abstract description 21
- -1 copper metal compound Chemical class 0.000 claims description 30
- 239000011889 copper foil Substances 0.000 claims description 26
- 238000003475 lamination Methods 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000007872 degassing Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000002905 metal composite material Substances 0.000 abstract 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010030 laminating Methods 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 54
- 230000004888 barrier function Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 102100023170 Nuclear receptor subfamily 1 group D member 1 Human genes 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an in-situ preparation method of a lithium-sulfur battery based on a silicon cathode. After a three-electrode lithium-sulfur laminated battery is prepared according to the laminating sequence of a lithium-sulfur battery anode plate, a lithium/copper metal composite electrode plate, a silicon electrode plate and a lithium/copper metal composite electrode plate, lithium is pre-stored for the silicon electrode plate by an in-situ lithium pre-storage method, and the lithium/copper metal composite electrode plate is taken out and packaged in situ after lithium pre-storage to obtain the lithium-sulfur battery taking the silicon electrode plate as the cathode. According to the method, the preparation process of the silicon based lithium-sulfur battery is simplified, the process of removing the battery, taking the electrode plates and repeatedly producing plates is omitted, the risk of failure of an existing process is avoided, and the method is easily transformed into industrial production technology.
Description
Technical field
The invention belongs to lithium-sulfur cell technical field, it is related to a kind of original position preparation side of the lithium-sulfur cell based on silicium cathode
Method.
Background technology
Lithium-sulfur cell is a kind of secondary chemical sources of electric energy of high-energy-density, with consumer electronics product, new-energy automobile
And the fast development in the field such as energy-storage system, lithium-sulfur cell receives much concern.The specific capacity of sulfur positive pole is up to 1675mAh/g, much
Material higher than commercial wide variety of cobalt acid lithium battery.The theoretical specific capacity of lithium metal is 3860mAh/g, and lithium-sulfur cell is managed
Be up to 2600Wh/kg by energy density, and sulfur be a kind of environment amenable element, environment is not polluted substantially it is considered to
Relatively low to the cost of sulfur, so, lithium-sulfur cell has extraordinary application prospect in electrokinetic cell of future generation.
Lithium-sulfur cell is used the sulfur-based compound with sulfur-sulfide linkage as positive active material, and the polysulfide of lithium is molten
In electrolyte, react with highly active lithium an- ode, easily cause shuttle effect, lead to active substance to lose, cause certainly
Electric discharge, affects cycle performance.
Lithium-sulfur cell typically does negative pole using metallic lithium foil, and lithium metal has higher chemical reactivity, and chemistry is unstable
Fixed, more with sulfur-based compound side reaction, produce self discharge；And, the fusing point of lithium is low, in the case of battery failure, easily with electrolysis
Matter, moisture, air vigorous reaction, produce blast；In addition, cathode of lithium is in cyclic process, it is also easy to produce dead band, Li dendrite, impact
Cycle performance of battery, or even Li dendrite can pierce through barrier film, lead to internal short-circuit.
For avoiding the negative effect of the lithium-sulfur cell that brings using lithium anode, non-lithium an- ode has obtained widely
Concern and research.Patent CN101465441 discloses the preparation method of a kind of lithium-sulfur cell with graphite as negative pole and this battery,
It supplements lithium source (storing up lithium in advance), negative pole is steady using the structure of no lithium source in advance by the method for Electrochemical lithiation in sulfur positive pole
Fixed graphite cathode, instead of highly active lithium metal, improves safety and the cyclical stability of lithium-sulfur cell.Patent
CN102694158A discloses a kind of preparation method of the lithium-sulfur cell of the siliceous cathode of lithium with excess deposition lithium, and this negative pole can drop
The formation probability of low Li dendrite, improves cycle performance of battery and security performance.
Containing silicium cathode, there is the theoretical capacity higher than cathode of lithium, the theoretical capacity of silicium cathode is 4198mAh/g, the sub- silicon of oxidation
Theoretical capacity be 1964mAh/g, lithium-sulfur cell is prepared using the cathode of lithium of alternative metals containing silicium cathode, lithium metal can be overcome
High chemical instability and the generation of Li dendrite, and safety and the cyclical stability of lithium-sulfur cell can be lifted.But,
The preparation of such non-lithium metal battery, needs to prepare pre- storage lithium electrode first, then takes battery apart, takes out pre- storage pole piece, so
Film-making again, is assembled into lithium-sulfur cell afterwards, and such battery preparation method is more complicated, and in preparation process, failure risk is big, and prepares step
Suddenly loaded down with trivial details condition harshness is unfavorable for commercial production, and more or less limits large-scale application.
Content of the invention
It is an object of the present invention to provide a kind of in-situ preparation method of the lithium-sulfur cell based on silicium cathode, this preparation method is controlled
Property high, simplify the preparation technology flow process of silicon substrate lithium-sulfur cell, evaded the failure risk of existing process, be easily converted into industrial life
Product technology.
The present invention is achieved in that a kind of in-situ preparation method of the lithium-sulfur cell based on silicium cathode, including step：
The first step：Prepare lithium/copper metal compound electric pole piece, this pole piece includes Copper Foil and is attached on Copper Foil as lithium
The lithium paper tinsel that the lithium metal in source is formed；
Second step：According to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, silicon-containing electrode piece and lithium/copper metal
The lamination order of compound electric pole piece carries out lamination, prepares three electrode lithium sulfur laminated batteries；
3rd step：Using the method that electrochemical in-situ stores up lithium in advance, silicon-containing electrode piece is carried out with pre- storage lithium；
4th step：After pre- storage lithium terminates, under gas shield environment, lithium/copper metal compound electric pole piece is taken out, then right
Pole group degasification is simultaneously directly sealed, and obtains the two electrode lithium-sulfur cells with silicon-containing electrode piece as negative pole.
In described lithium/copper metal compound electric pole piece, described Copper Foil makes as the structural support of lithium metal, collector and lug
With；Or use as lug.
When described Copper Foil uses as the structural support of lithium metal, collector and lug, the capacity of lithium paper tinsel/silicon-containing electrode piece
Than for 1-10；When described Copper Foil uses as lug, the Capacity Ratio of lithium paper tinsel/silicon-containing electrode piece is 2-10.
The thickness of described lithium paper tinsel is 10-200 micron, and the thickness of Copper Foil is 5-20 micron.
Described silicon-containing electrode piece includes the silicon electrode piece that active substance is elementary silicon and the oxygen that active substance is the sub- silicon of oxidation
Change sub- silicon electrode piece.
In second step, during electrode lamination, the lug of positive pole plate of lithium-sulfur cell and silicon-containing electrode piece, in battery the same side, is made
First side for battery；The lug of lithium/copper electrode piece in the relative side in first side, as the caudal of battery.
In 3rd step, silicon-containing electrode piece is carried out with pre- storage lithium is with silicon-containing electrode piece as positive pole, with lithium/copper metal compound electric
Pole piece is negative pole, stores up lithium in advance using electrochemical in-situ method.
Wherein, lithium is stored up in advance using electrochemical in-situ method, using the method for constant current discharge, discharge-rate is 0.01C-
10C, blanking voltage is 0.2-0 volt；Or the method using constant voltage, discharge voltage is 0.2-0 volt, and cut-off current is
0.001C-0.1C；Or use constant current, the method for constant voltage combined discharge, galvanostatic conditions, discharge-rate is 0.01C-10C,
Blanking voltage is 0.2-0 volt, constant voltage condition, and discharge voltage is 0.2-0 volt, and cut-off current is 0.001C-0.1C.
In 3rd step, described gas shield environment is nitrogen or argon environmental protection.
The in-situ preparation method based on the lithium-sulfur cell containing silicium cathode that the present invention provides, by three electrode lithium-sulfur cell bodies
The foundation of system, carries out original position pre- storage lithium, and the method eliminates tears battery open, takes out pre- storage pole piece, the mistake replicating for pole piece of laying equal stress on
Journey, overcomes and tears battery open, the pre- pole piece of storing up of taking-up lays equal stress on duplication for the failure risk during pole piece, simplifies lithium-sulfur cell
Preparation flow, evaded process failure risk.This preparation method technique is simpler, is conducive to the production of lithium-sulfur cell to promote,
There is great production practices meaning.
Brief description
Fig. 1 is the pre- storage lithium curve of the embodiment of the present invention 1；
Fig. 2 is the schematic diagram of three electrode lithium-sulfur cells of the embodiment of the present invention 1,3 preparation；
Fig. 3 is the schematic cross-section of three electrode lithium-sulfur cells of the embodiment of the present invention 1,3 preparation；
Fig. 4 is the schematic cross-section of the two poles of the earth lithium-sulfur cell of final preparation in the embodiment of the present invention 1,2,3；
Fig. 5 is the pre- storage lithium curve of the embodiment of the present invention 2；
Fig. 6 is the pre- storage lithium curve of the embodiment of the present invention 3.
Specific embodiment
Below, in conjunction with example, the substantive distinguishing features of the present invention and advantage are further described, but the present invention not office
It is limited to listed embodiment.
Embodiment 1
A kind of in-situ preparation method based on the lithium-sulfur cell containing silicium cathode, in lithium/copper metal compound electric pole piece, Copper Foil is made
To use for the structural support of lithium metal, collector and lug, to use pure silicon negative pole containing silicium cathode, embodiment step is as follows：
(1) prepare that lithium/copper metal compound electric pole piece is stand-by first, this pole piece is made up of metallic lithium foil and Copper Foil, by metal
Lithium paper tinsel is attached at the two sides of Copper Foil and reserves lug (other parts two sides in addition to lug for the Copper Foil is covered by metallic lithium foil), is obtained
Described lithium/copper metal compound electric pole piece；
Wherein, the thickness of lithium paper tinsel is 40 microns, and the thickness of Copper Foil is 8 microns, and the Capacity Ratio of lithium paper tinsel/silicon-containing electrode piece is 3；
In addition, according to the preparation technology flow process of lithium-sulfur cell, prepare positive pole plate of lithium-sulfur cell, silicon-containing electrode piece, barrier film,
Lug, battery case, electrolyte etc. are stand-by.
It should be noted that, positive pole plate of lithium-sulfur cell, silicon-containing electrode piece, barrier film, lug, battery case, electrolyte etc. are
Conventional material or customary preparation methods preparation.
(2) it is combined according to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, silicon-containing electrode piece and lithium/copper metal
The lamination order of electrode slice carries out lamination, prepares three electrode lithium sulfur laminated batteries；
During electrode lamination, the lug of positive pole plate of lithium-sulfur cell and silicon-containing electrode piece in battery the same side, as battery
First side, the lug of lithium/copper electrode piece in the relative side in first side, as the caudal of battery.
(3) method storing up lithium in advance using electrochemical in-situ, carries out pre- storage lithium to silicon-containing electrode, electrochemical pre-treatment, to contain
Silicon electrode piece is positive pole, with lithium/copper compound electric pole piece as negative pole, can be using the side of constant current discharge and constant voltage discharge combination
Formula, galvanostatic conditions, discharge-rate is 0.1C, and blanking voltage is 0.005 volt, constant voltage condition, and discharge voltage is 0.005 volt
Spy, cut-off current is 0.02C.
(4), after pre- storage lithium terminates, under argon dry environment, lithium/copper metal compound electric pole piece is taken out, then to pole group
Degasification is simultaneously directly sealed, and obtains the two electrode lithium-sulfur cells with silicon-containing electrode piece as negative pole.
Embodiment 2
A kind of in-situ preparation method based on the lithium-sulfur cell containing silicium cathode, in lithium/copper metal compound electric pole piece, Copper Foil is made
To use for lug, to use pure silicon negative pole containing silicium cathode, embodiment step is as follows：
(1) prepare that lithium/copper metal compound electric pole piece is stand-by first, this pole piece is made up of metallic lithium foil and Copper Foil, by metal
Lithium paper tinsel is attached with the Copper Foil phase as lug, and described lithium/copper metal compound electric pole piece is obtained；
Wherein, the thickness of lithium paper tinsel is 200 microns, and the thickness of Copper Foil is 8 microns, and the Capacity Ratio of lithium paper tinsel/silicon-containing electrode piece is
5；
In addition, according to the preparation technology flow process of lithium-sulfur cell, prepare positive pole plate of lithium-sulfur cell, silicon-containing electrode piece, barrier film,
Lug, battery case, electrolyte etc. are stand-by；
It should be noted that, positive pole plate of lithium-sulfur cell, silicon-containing electrode piece, barrier film, lug, battery case, electrolyte etc. are
Conventional material or customary preparation methods preparation.
(2) it is combined according to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, silicon-containing electrode piece and lithium/copper metal
The lamination order of electrode slice carries out lamination, prepares three electrode lithium sulfur laminated batteries；
During electrode lamination, the lug of positive pole plate of lithium-sulfur cell and silicon-containing electrode piece in battery the same side, as battery
First side, the lug of lithium/copper electrode piece in the relative side in first side, as the caudal of battery.
(3) method storing up lithium in advance using electrochemical in-situ, carries out pre- storage lithium to silicon-containing electrode, electrochemical pre-treatment, to contain
Silicon electrode piece is positive pole, with lithium/copper compound electric pole piece as negative pole, by the way of constant current discharge, galvanostatic conditions, and electric discharge times
Rate is 0.05C, and blanking voltage is 0.001 volt.
(4), after pre- storage lithium terminates, under argon dry environment, lithium/copper metal compound electric pole piece is taken out, then to pole group
Degasification is simultaneously directly sealed, and obtains the two electrode lithium-sulfur cells with silicon-containing electrode piece as negative pole.
Embodiment 3
A kind of in-situ preparation method based on the lithium-sulfur cell containing silicium cathode, in lithium/copper metal compound electric pole piece, Copper Foil is made
To use for the structural support of lithium metal, collector and lug, containing silicium cathode using the graphite cathode containing 6% silicon materials, to implement
Example step is as follows：
(1) prepare that lithium/copper metal compound electric pole piece is stand-by first, this pole piece is made up of metallic lithium foil and Copper Foil, by metal
Lithium paper tinsel is attached at Copper Foil two sides and reserves lug (other parts two sides in addition to lug for the Copper Foil is covered by metallic lithium foil), prepared institute
State lithium/copper metal compound electric pole piece；
Wherein, the thickness of lithium paper tinsel is 40 microns, and the thickness of Copper Foil is 8 microns, and the Capacity Ratio of lithium paper tinsel/silicon-containing electrode piece is 3；
In addition, according to the preparation technology flow process of lithium-sulfur cell, prepare positive pole plate of lithium-sulfur cell, silicon-containing electrode piece, barrier film,
Lug, battery case, electrolyte etc. are stand-by.
It should be noted that, positive pole plate of lithium-sulfur cell, silicon-containing electrode piece, barrier film, lug, battery case, electrolyte etc. are
Conventional material or customary preparation methods preparation.
(2) it is combined according to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, silicon-containing electrode piece and lithium/copper metal
The lamination order of electrode slice carries out lamination, prepares three electrode lithium sulfur laminated batteries；
During electrode lamination, the lug of positive pole plate of lithium-sulfur cell and silicon-containing electrode piece in battery the same side, as battery
First side, the lug of lithium/copper electrode piece in the relative side in first side, as the caudal of battery.
(3) method storing up lithium in advance using electrochemical in-situ, carries out pre- storage lithium to silicon-containing electrode, electrochemical pre-treatment, to contain
Silicon electrode piece is positive pole, with lithium/copper compound electric pole piece as negative pole, can be using the side of constant current discharge and constant voltage discharge combination
Formula, galvanostatic conditions, discharge-rate is 0.1C, and blanking voltage is 0.005 volt, constant voltage condition, and discharge voltage is 0.005 volt
Spy, cut-off current is 0.02C.
(4), after pre- storage lithium terminates, under argon dry environment, lithium/copper metal compound electric pole piece is taken out, then to pole group
Degasification is simultaneously directly sealed, and obtains the two electrode lithium-sulfur cells with silicon-containing electrode piece as negative pole.
Fig. 2 shows the outline drawing of three electrode lithium-sulfur cells of the embodiment of the present invention 1,3 preparation, including anode ear 1, siliceous
The silicium cathode lug 2 of electrode slice and the lug 3 of lithium/copper metal compound electric pole piece.
Fig. 3 shows the sectional view of three electrode lithium-sulfur cells of the embodiment of the present invention 1,3 preparation, includes lithium/copper metal
Compound electric pole piece 7, battery positive pole piece 6 and silicon-containing electrode piece 5, lithium/copper metal compound electric pole piece 7 is in battery positive pole piece 6
And between silicon-containing electrode piece 5, lithium/copper metal compound electric pole piece 7, battery positive pole piece 6 and silicon-containing electrode piece 5 by barrier film
4 separate and carry out lamination.
If it should be noted that Copper Foil is only used as lug when using, situation in example 2, then in figure 3
Lithium/copper metal compound electric pole piece 7 is to be replaced by lithium piece, and in embodiment 2, the sectional view of three electrode lithium-sulfur cells of preparation is other
Structure is as shown in Figure 2.
Fig. 4 shows the sectional view of the lithium-sulfur cell of the embodiment of the present invention 1,2,3 preparation, including silicon-containing electrode piece
5th, battery positive pole piece 6 and the barrier film 4 being spaced apart by silicon-containing electrode piece 5 and battery positive pole piece 6.
The above is only the preferred embodiment of the present invention it is noted that ordinary skill people for the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of in-situ preparation method of the lithium-sulfur cell based on silicium cathode is it is characterised in that include step：
The first step：Prepare lithium/copper metal compound electric pole piece, this pole piece includes Copper Foil and is attached on Copper Foil as lithium source
The lithium paper tinsel that lithium metal is formed；
Second step：It is combined according to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, silicon-containing electrode piece and lithium/copper metal
The lamination order of electrode slice carries out lamination, prepares three electrode lithium sulfur laminated batteries；
3rd step：Using the method that electrochemical in-situ stores up lithium in advance, silicon-containing electrode piece is carried out with pre- storage lithium；
4th step：After pre- storage lithium terminates, under gas shield environment, lithium/copper metal compound electric pole piece is taken out, then to pole group
Degasification is simultaneously directly sealed, and obtains the two electrode lithium-sulfur cells with silicon-containing electrode piece as negative pole.
2. preparation method as claimed in claim 1 is it is characterised in that in described lithium/copper metal compound electric pole piece, described Copper Foil
Use as the structural support of lithium metal, collector and lug；Or use as lug.
3. preparation method as claimed in claim 2 is it is characterised in that described Copper Foil is as the structural support of lithium metal, afflux
When body and lug use, the Capacity Ratio of lithium paper tinsel/silicon-containing electrode piece is 1-10；When described Copper Foil uses as lug, lithium paper tinsel/siliceous
The Capacity Ratio of electrode slice is 2-10.
4. preparation method as claimed in claim 1 it is characterised in that described lithium paper tinsel thickness be 10-200 micron, described copper
The thickness of paper tinsel is 5-20 micron.
5. preparation method as claimed in claim 1 is it is characterised in that it is elementary silicon that described silicon-containing electrode piece includes active substance
Silicon electrode piece and oxidation Asia silicon electrode piece that active substance is the sub- silicon of oxidation.
6. preparation method as claimed in claim 1 is it is characterised in that in second step, during electrode lamination, positive pole plate of lithium-sulfur cell
With the lug of silicon-containing electrode piece in battery the same side, as the first side of battery；The lug of lithium/copper electrode piece first side relative one
Side, as the caudal of battery.
7. preparation method as claimed in claim 1 is it is characterised in that in the 3rd step, silicon-containing electrode piece is carried out pre- storage lithium be with
Silicon-containing electrode piece be positive pole, with lithium/copper metal compound electric pole piece as negative pole, lithium is stored up in advance using electrochemical in-situ method.
8. preparation method as claimed in claim 7 is it is characterised in that store up lithium in advance using electrochemical in-situ method, using constant current
The method of electric discharge；Or adopt the method for constant voltage or use constant current, the method for constant voltage combined discharge.
9. preparation method as claimed in claim 1 is it is characterised in that in the 3rd step, described gas shield environment is nitrogen or argon
Gas shielded environment.
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