CN106785075B - A kind of in-situ preparation method of the lithium-sulfur cell based on graphite cathode - Google Patents
A kind of in-situ preparation method of the lithium-sulfur cell based on graphite cathode Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 54
- 239000010439 graphite Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 110
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- 239000010949 copper Substances 0.000 claims abstract description 39
- -1 copper metal compound Chemical class 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 20
- 238000003475 lamination Methods 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 29
- 239000011889 copper foil Substances 0.000 claims description 21
- 239000011888 foil Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 238000002848 electrochemical method Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 description 40
- 239000003792 electrolyte Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- 208000032953 Device battery issue Diseases 0.000 description 1
- 102100023170 Nuclear receptor subfamily 1 group D member 1 Human genes 0.000 description 1
- 206010044565 Tremor Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000005056 cell body Anatomy 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
- 150000001880 copper compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- 238000004880 explosion Methods 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000047 product 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
- 238000006467 substitution reaction Methods 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
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
The present invention discloses a kind of in-situ preparation method of lithium-sulfur cell based on graphite cathode.The present invention is first, in accordance with positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, graphite electrode piece and lithium/copper metal compound electric pole piece lamination sequence, prepare three electrode lithium sulphur laminated batteries, using the method for pre- storage lithium in situ, pre- storage lithium is carried out to graphite electrode piece；After pre- storage lithium, lithium/copper metal compound electric pole piece is taken out and is packaged in situ, is obtained using graphite electrode piece as the lithium-sulfur cell of cathode.The preparation method simplifies the preparation process flow of graphite-based lithium-sulfur cell, saves and tears battery open, takes pole piece and repeat the process of film-making, has evaded the failure risk of prior art, be easily converted into industrial production technology.
Description
Technical field
The invention belongs to lithium-sulfur cell technical fields, are related to a kind of side of being prepared in situ of lithium-sulfur cell based on graphite cathode
Method.
Background technique
In recent years, the fast development in the fields such as consumer electronics product, new-energy automobile and energy-storage system, to secondary cell
Increase in demand, particularly, battery energy density is required it is higher and higher, it is more succinct, lighter to adapt to energy storage equipment
Development trend.
Lithium-sulfur cell is a kind of lithium battery using element sulphur as anode.Specific capacity is up to 1675mAh/g, much high
In the material of commercial widely applied cobalt acid lithium battery.And sulphur is a kind of environment amenable element, is not had substantially to environment
There is pollution, it is contemplated that cost is relatively low for sulphur, so, lithium-sulfur cell is a kind of very promising lithium battery.
Lithium-sulfur cell, which uses, has sulphur-sulfide linkage sulfur-based compound as a positive electrode active material, and the polysulfide of lithium is molten
In electrolyte, polysulfide is reacted with lithium an- ode, easily causes shuttle effect, active material is caused to lose, and influences to recycle
Performance.
Lithium-sulfur cell generally uses metallic lithium foil to do cathode, lithium metal chemical reactivity with higher, chemistry shakiness
It is fixed, it is more with sulfur-based compound side reaction, generate self discharge；Moreover, the fusing point of lithium is low, in the case of battery failure, easily with electrolysis
Matter, moisture, air vigorous reaction generate explosion；In addition, cathode of lithium in cyclic process, is also easy to produce dead zone, Li dendrite, influence
Cycle performance of battery or even Li dendrite can pierce through diaphragm, lead to internal short-circuit.
To avoid the effect negative using lithium anode bring lithium-sulfur cell, non-lithium an- ode has been obtained widely
Concern and research.Patent CN101465441 disclose it is a kind of using graphite as the preparation method of the lithium-sulfur cell of cathode and the battery,
It supplements lithium source (storing up lithium in advance) in sulphur anode in advance, cathode is steady using the structure without lithium source by the method for Electrochemical lithiation
Fixed graphite cathode improves safety and the cyclical stability of lithium-sulfur cell instead of the lithium metal of high activity.
Lithium-sulfur cell is prepared using graphite cathode substitution lithium anode, overcomes the high chemical instability of lithium metal
And the generation of Li dendrite, and safety and the cyclical stability of lithium-sulfur cell can be promoted.But such non-lithium metal battery
Preparation, need to prepare pre- storage lithium electrode first, then dismantle battery, take out pre- storage pole piece, then film-making again, is assembled into lithium
Sulphur battery, such battery preparation method is more complex, and failure risk is big in preparation process, and the cumbersome condition harshness of preparation step is unfavorable
In industrial production, more or less limits large-scale application.
Summary of the invention
The object of the present invention is to provide a kind of in-situ preparation methods of lithium-sulfur cell based on graphite cathode.The preparation method
Controllability is high, simplifies the preparation process flow of graphite-based lithium-sulfur cell, has evaded the failure risk of prior art, be easily converted into
Industrial production technology.
To achieve the above object, the present invention adopts the following technical scheme:
The invention is realized in this way a kind of in-situ preparation method of the lithium-sulfur cell based on graphite cathode, including it is following
Step:
Step 1: preparing lithium/copper metal compound electric pole piece, the lithium/copper metal compound electric pole piece includes copper foil and attaching
Lithium foil made of lithium metal on the copper foil as lithium source；
Step 2: according to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, graphite electrode piece and lithium/copper metal
The lamination sequence of compound electric pole piece carries out lamination, prepares three electrode lithium sulphur laminated batteries；
Step 3: the method for storing up lithium in advance using electrochemical in-situ carries out pre- storage lithium to graphite electrode piece；
Step 4: under protective atmosphere environment, lithium/copper metal compound electric pole piece is taken out after storage lithium in advance, it is then right
Pole group degasification is simultaneously directly sealed, and the two electrode lithium-sulfur cells using graphite electrode piece as cathode are obtained.
In the lithium/copper metal compound electric pole piece, the copper foil makes as the structural support of lithium metal, collector and tab
With；Or it is used as tab.
The copper foil is as the structural support of lithium metal, collector and tab in use, lithium foil/graphite electrode piece capacity
Than for 1-10；The copper foil is as tab in use, lithium foil/graphite electrode piece capacity ratio is 2-10.
The lithium foil with a thickness of 10-200 microns, copper foil with a thickness of 5-20 microns.
In second step, when electrode lamination, the tab of positive pole plate of lithium-sulfur cell and graphite electrode piece is made in battery the same side
For the first side of battery；Lithium/copper metal compound electric pole piece tab side opposite in first side, the caudal as battery.
In third step, carrying out pre- storage lithium to graphite electrode piece is with graphite electrode piece for anode, with lithium/copper metal compound electric
Pole piece is cathode, stores up lithium in advance using electrochemical method.
In third step, the method for storing up lithium in advance using electrochemical method, using the method for constant current discharge, discharge-rate is
0.01C-10C, blanking voltage are 0.2-0 volts；Or the method using constant voltage, discharge voltage are 0.2-0 volts, cut-off current
For 0.001C-0.1C；Or use constant current, the method for constant voltage combined discharge, galvanostatic conditions, discharge-rate 0.01C-
10C, blanking voltage are 0.2-0 volts, and constant voltage condition, discharge voltage is 0.2-0 volts, cut-off current 0.001C-0.1C.
In 4th step, the protective atmosphere environment refers to nitrogen or argon gas.
The in-situ preparation method of lithium-sulfur cell provided by the invention based on graphite cathode passes through three electrode lithium-sulfur cell bodies
The foundation of system carries out pre- storage lithium in situ, and this method eliminates and tears battery open, the pre- storage pole piece of taking-up lays equal stress on and replicates the mistake of standby pole piece
Journey overcomes and tears battery open, takes out pre- storage pole piece and lay equal stress on the failure risk during replicating standby pole piece, simplifies lithium-sulfur cell
Preparation flow.The preparation method technique is simpler, and the production for being conducive to lithium-sulfur cell is promoted, and has great production practices meaning
Justice.
Detailed description of the invention
Fig. 1 is lithium/copper foil metal composite electrode slice schematic diagram prepared by the embodiment of the present invention 1；
Fig. 2 is the pre- storage lithium curve of the embodiment of the present invention 1；
Fig. 3 is the appearance schematic diagram of three electrode lithium-sulfur cells prepared by the embodiment of the present invention 1；
Fig. 4 is three electrode lithium-sulfur cell schematic cross-sections prepared by the embodiment of the present invention 1；
Fig. 5 is the lithium-sulfur cell schematic cross-section finally prepared in the embodiment of the present invention 1；
Fig. 6 is the appearance schematic diagram of the lithium-sulfur cell finally prepared in the embodiment of the present invention 1；
Fig. 7 is lithium/copper polar ear metal composite electrode slice schematic diagram prepared by the embodiment of the present invention 2；
Fig. 8 is the pre- storage lithium curve of the embodiment of the present invention 2.
Specific embodiment
In the following, in conjunction with example, property feature and advantage is further described for the essence of the present invention, but the present invention not office
It is limited to listed embodiment.
Embodiment 1
A kind of in-situ preparation method of the lithium-sulfur cell based on graphite cathode, in lithium/copper metal compound electric pole piece, copper foil is made
Come for the structural support of lithium metal, collector and tab using embodiment step is as follows:
(1) the lithium foil 2 and copper foil 1 that lithium/copper metal compound electric pole piece is stand-by, which is fabricated to by lithium metal are prepared first
Metallic lithium foil is attached at 1 two sides of copper foil and reserves tab (other parts two sides of the copper foil in addition to tab is by metallic lithium foil by composition
Covering), the lithium/copper metal compound electric pole piece is made；Wherein, lithium foil with a thickness of 40 microns, copper foil with a thickness of 8 microns,
Lithium foil/graphite electrode piece capacity ratio is 3；
In addition, according to the preparation process flow of lithium-sulfur cell, prepare positive pole plate of lithium-sulfur cell, graphite electrode piece, diaphragm,
Tab, battery case, electrolyte etc. are stand-by.
It should be noted that positive pole plate of lithium-sulfur cell, graphite electrode piece, diaphragm, tab, battery case, electrolyte etc. are
Conventional material or customary preparation methods preparation.
(2) compound according to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, graphite electrode piece and lithium/copper metal
The lamination sequence of electrode slice carries out lamination, prepares three electrode lithium sulphur laminated batteries；Shape is as shown in figure 3, include anode ear 3, stone
The graphite cathode tab 4 and lithium of black negative electrode tab/copper metal compound electric pole piece tab 5, sectional view is as shown in figure 4, include
Graphite electrode piece 6, positive plate 7 and lithium/copper metal compound electric pole piece 8, lithium/copper metal compound electric pole piece 8 are placed in graphite electrode
It is spaced from each other between piece 6, positive plate 7 and by diaphragm 9.
When electrode lamination, the tab of positive pole plate of lithium-sulfur cell and graphite electrode piece is in battery the same side, as battery
First side, lithium/copper metal electrode slice tab side opposite in first side, the caudal as battery.
(3) method for storing up lithium in advance using electrochemical in-situ carries out pre- storage lithium, electrochemical pre-treatment, with stone to graphite electrode
Electrode ink piece is anode, is negative pole with lithium/copper compound electric pole piece, the side that can be combined using constant current discharge and constant voltage discharge
Formula, galvanostatic conditions, discharge-rate 0.1C, blanking voltage are 0.005 volt, and constant voltage condition, discharge voltage is 0.005 volt
Spy, cut-off current 0.02C.
(4) under argon gas dry environment, lithium/copper metal compound electric pole piece is taken out, then to pole group after storage lithium in advance
Degasification is simultaneously directly sealed, and obtains the two electrode lithium-sulfur cells using graphite electrode piece as cathode, sectional view is as shown in figure 5, include
Graphite electrode piece 6, positive plate 7 and diaphragm 9, graphite electrode piece 6, positive plate 7 are separated by diaphragm 9, and shape is as shown in fig. 6, packet
Include anode ear 3 and graphite electrode negative electrode lug 4.
Embodiment 2
A kind of in-situ preparation method of the lithium-sulfur cell based on graphite cathode, in lithium/copper metal compound electric pole piece, copper foil is made
Come for tab using embodiment step is as follows:
(1) it is stand-by that lithium/copper metal compound electric pole piece is prepared first, pole piece lithium foil 2 and copper foil shape made of lithium metal
At copper polar ear 1 form, by metallic lithium foil with as tab copper foil attach, the lithium/copper metal compound electric pole piece is made；Its
In, lithium foil with a thickness of 200 microns, copper foil with a thickness of 8 microns, lithium foil/graphite electrode capacity ratio is 5；
In addition, according to the preparation process flow of lithium-sulfur cell, prepare positive pole plate of lithium-sulfur cell, graphite electrode piece, diaphragm,
Tab, battery case, electrolyte etc. are stand-by.
It should be noted that positive pole plate of lithium-sulfur cell, graphite electrode piece, diaphragm, tab, battery case, electrolyte etc. are
Conventional material or customary preparation methods preparation.
(2) compound according to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, graphite electrode piece and lithium/copper metal
The lamination sequence of electrode slice carries out lamination, prepares three electrode lithium sulphur laminated batteries；
When electrode lamination, the tab of positive pole plate of lithium-sulfur cell and graphite electrode piece is in battery the same side, as battery
First side, lithium/copper metal electrode slice tab side opposite in first side, the caudal as battery.
(3) method for storing up lithium in advance using electrochemical in-situ carries out pre- storage lithium, electrochemical pre-treatment, with stone to graphite electrode
Electrode ink piece is anode, is negative pole with lithium/copper metal compound electric pole piece, by the way of constant current discharge, galvanostatic conditions are put
Electric multiplying power is 0.05C, and blanking voltage is 0.001 volt.
(4) under argon gas dry environment, lithium/copper metal compound electric pole piece is taken out, then to pole group after storage lithium in advance
Degasification is simultaneously directly sealed, and the two electrode lithium-sulfur cells using graphite electrode piece as cathode are obtained.
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 (8)
1. a kind of in-situ preparation method of the lithium-sulfur cell based on graphite cathode, which comprises the following steps:
Step 1: prepare lithium/copper metal compound electric pole piece, the lithium/copper metal compound electric pole piece includes copper foil and is attached at copper
Lithium foil made of lithium metal on foil as lithium source；
Step 2: compound according to positive pole plate of lithium-sulfur cell, lithium/copper metal compound electric pole piece, graphite electrode piece and lithium/copper metal
The lamination sequence of electrode slice carries out lamination, prepares three electrode lithium sulphur laminated batteries；
Step 3: the method for storing up lithium in advance using electrochemical in-situ carries out pre- storage lithium to graphite electrode piece；
Step 4: under protective atmosphere environment, lithium/copper metal compound electric pole piece is taken out, then to pole group after storage lithium in advance
Degasification is simultaneously directly sealed, and the two electrode lithium-sulfur cells using graphite electrode piece as cathode are obtained.
2. preparation method as described in claim 1, which is characterized in that in the lithium/copper metal compound electric pole piece, the copper foil
It is used as the structural support of lithium metal, collector and tab；Or it is used as tab.
3. preparation method as claimed in claim 2, which is characterized in that structural support of the copper foil as lithium metal, afflux
Body and tab are in use, lithium foil/graphite electrode piece capacity ratio is 1-10；The copper foil is as tab in use, lithium foil/graphite
The capacity ratio of electrode slice is 2-10.
4. preparation method as described in claim 1, which is characterized in that the lithium foil with a thickness of 10-200 microns, copper foil
With a thickness of 5-20 microns.
5. preparation method as described in claim 1, which is characterized in that in second step, when electrode lamination, lithium-sulphur cell positive electrode pole
First side of the tab of piece and graphite electrode piece in battery the same side, as battery；Lithium/copper metal compound electric pole piece tab is in head
The opposite side in side, the caudal as battery.
6. preparation method as described in claim 1, which is characterized in that in third step, carrying out pre- storage lithium to graphite electrode piece is
It is anode with graphite electrode piece, is negative pole with lithium/copper metal compound electric pole piece, lithium is stored up using electrochemical method in advance.
7. preparation method as claimed in claim 6, which is characterized in that in third step, store up the side of lithium in advance using electrochemical method
Method using the method for constant current discharge, or using the method for constant voltage, or uses constant current, the side of constant voltage combined discharge
Method.
8. preparation method as described in claim 1, which is characterized in that in the 4th step, the protective atmosphere environment refers to nitrogen
Or argon gas.
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| CN107819104B (en) * | 2017-09-27 | 2020-06-26 | 天津力神电池股份有限公司 | Preparation method of lithium-copper composite negative electrode foil |
| US20200395593A1 (en) * | 2019-06-12 | 2020-12-17 | A123 Systems Llc | Anode pre-lithiation for high energy li-ion battery |
| CN111366852A (en) * | 2020-03-26 | 2020-07-03 | 上海电气集团股份有限公司 | In-situ observation method and device for charging state of graphite electrode |
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| CN102694196A (en) * | 2012-05-16 | 2012-09-26 | 大连丽昌新材料有限公司 | Lithium sulphur battery and manufacturing method thereof |
| WO2016159058A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Lithium ion secondary battery and method of manufacturing same |
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| CN102694196A (en) * | 2012-05-16 | 2012-09-26 | 大连丽昌新材料有限公司 | Lithium sulphur battery and manufacturing method thereof |
| WO2016159058A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Lithium ion secondary battery and method of manufacturing same |
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