CN108899584A - A kind of production method of high specific energy Soft Roll lithium-sulfur cell - Google Patents

A kind of production method of high specific energy Soft Roll lithium-sulfur cell Download PDF

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CN108899584A
CN108899584A CN201810670455.2A CN201810670455A CN108899584A CN 108899584 A CN108899584 A CN 108899584A CN 201810670455 A CN201810670455 A CN 201810670455A CN 108899584 A CN108899584 A CN 108899584A
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lithium
sulphur
pole piece
carbon
obtains
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罗迪
李润秋
姚瑾
焦熠琨
张鹭
杨蓉
付欣
任冰
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State Grid Corp of China SGCC
Economic and Technological Research Institute of State Grid Shaanxi Electric Power Co Ltd
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State Grid Corp of China SGCC
Economic and Technological Research Institute of State Grid Shaanxi Electric Power Co Ltd
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/362—Composites
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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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  • General Chemical & Material Sciences (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention discloses a kind of production methods of high specific energy Soft Roll lithium-sulfur cell, include the following steps：1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；2) mixed-powder is reacted, obtains sulphur/carbon composite；3) ball milling is carried out after setting middle addition metal oxide to sulphur/carbon composite, obtains metal oxide-sulphur/carbon composite；4) pole piece is obtained；5) anode pole piece；6) cathode pole piece；7) there must be the ceramic diaphragm of single side coating；8) ceramic diaphragm with single side coating is folded, then anode pole piece is held among the ceramic diaphragm with single side coating, be then superimposed again with cathode pole piece, obtain battery core；9) single battery is obtained, single battery is then subjected to pre-arcing and aging process；10) Vacuum Package and cutting edge are carried out, high specific energy Soft Roll lithium-sulfur cell is obtained, the first discharge specific capacity and cycle performance of the lithium-sulfur cell of this method production are more excellent.

Description

A kind of production method of high specific energy Soft Roll lithium-sulfur cell
Technical field
The invention belongs to lithium-sulfur cell fields, are related to a kind of production method of high specific energy Soft Roll lithium-sulfur cell.
Background technique
The arriving of Internet era, the fast development of electric car, large-scale energy-accumulating power station, all to lithium ion secondary battery More stringent requirements are proposed for performance, but existing secondary lithium battery is limited by own material properties and has been insufficient for needing It asks.Lithium-sulfur cell is due to having up to 1680
mA·h·g-1Theoretical specific capacity and 2600Whkg-1Theoretical energy density and active material sulphur valence Outstanding advantages of lattice are cheap, resourceful and hypotoxicity, it is considered to be a kind of very with the secondary cell system of application prospect.
However, sulphur is electronics and ion insulator, it is difficult to be used alone as positive electrode.In addition, lithium-sulfur cell is filling Positive sulfur materials can generate different intermediate products in discharge process, i.e., more sulphions are soluble to cause to live in the electrolyte Property the loss of substance sulphur, and the more sulphions of intermediate product diffuse to form " shuttle effect " between positive and negative anodes, cause battery from putting Electricity, coulombic efficiency is low and poor circulation.The actuals metaplasia that these problems limit lithium-sulfur cell produces.
Many researchs are all limited in the modification of battery single part at present, fail to go out from the angle of battery whole system Hair, is modified anode, cathode, diaphragm compound, therefore the first discharge specific capacity of lithium-sulfur cell and cycle performance are poor.
Summary of the invention
It is an object of the invention to overcome the above-mentioned prior art, a kind of high specific energy Soft Roll lithium-sulfur cell is provided Production method, the first discharge specific capacity and cycle performance of the lithium-sulfur cell of this method production are more excellent.
In order to achieve the above objectives, the production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains Metal oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with it is viscous It is coated on plus plate current-collecting body after tying agent A and solvent A mixing, is cut after drying, obtain pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, must has after drying The ceramic diaphragm of single side coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on and has Among the ceramic diaphragm of single side coating, wherein the side of coating and anode pole piece on the ceramic diaphragm side with single side coating Face is in contact, and positive pole ear is located at outside the ceramic diaphragm with single side coating, and the cathode pole piece then obtained again with step 6) is folded It is added together, obtains battery core；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains monomer electricity Then single battery is carried out pre-arcing and aging process by pond；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, is then cut out Side obtains high specific energy Soft Roll lithium-sulfur cell.
The mass ratio of carbon material and sublimed sulfur is (2~10) in step 1):1.
The content of metal oxide is (2~30) wt% in metal oxide-sulphur/carbon composite in step 3).
Metal oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is (95~55) in step 4): (2~35):(3~10)；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A consolidating for mixture contain Amount is (40~70) %；
Conductive agent B and binder B mass ratio are 1 in step 7):(0.5~2), conductive agent B, binder B and solvent B mixing The solid content of the mixture formed afterwards is 20%~40%.
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and (120~ DEG C 170) insulation reaction (5~20) h at a temperature of, then cooled to room temperature；
The time of ball milling is (30~300) min in step 3)；
Drying in step 4) uses vacuum drying mode, and drying temperature is (40-120) DEG C, and drying time is (2- 12)h；
The time of ball milling is (30~300) min in step 4).
Carbon material is one of KS-6, graphene, carbon nanotube, carbon fiber and porous carbon or a variety of mixes in any proportion The mixture of conjunction.
Metal oxide is Mg0.6Ni0.4O and Co3O4One or both of the mixture that mixes in any proportion.
Conductive agent A is one of Super P, KS-6, graphene, carbon nanotube, carbon fiber and porous carbon or a variety of presses The mixture of arbitrary proportion mixing；
Conductive agent B is one of Super P, KS-6, graphene, carbon nanotube, carbon fiber and porous carbon or a variety of presses The mixture of arbitrary proportion mixing.
Binder A is one of PVDF, PTFE, PEO, SBR and CMC or a variety of mixtures mixed in any proportion；
Binder B is one of PVDF, PTFE, PEO, SBR and CMC or a variety of mixtures mixed in any proportion；
Solvent A is the mixture that one or both of NMP and deionized water are mixed in any proportion；
Solvent B is the mixture that one or both of NMP and deionized water are mixed in any proportion.
Plus plate current-collecting body is three-dimensional porous aluminium foil or three-dimensional foam aluminium；
Negative current collector is three-dimensional porous copper foil or three-dimensional foam copper；
Cathode of lithium is three-dimensional porous lithium, three-dimensional foam lithium, three-dimensional porous copper/lithium metal or three-dimensional foam copper/lithium metal.
The invention has the advantages that：
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention is when specific operation, by compound to sulphur/carbon Metal oxide, which is added, in material not only can effectively improve active sulfur to obtain metal oxide-sulphur/carbon composite Utilization rate can also adsorb the electric discharge more lithium sulfides of intermediate product, inhibit the dissolution and migration of more lithium sulfides in the electrolytic solution, reduce Influence of the shuttle effect to battery performance.In addition, the ceramic diaphragm with single side coating is folded in the present invention, then will Anode pole piece is held among the ceramic diaphragm with single side coating, wherein on the ceramic diaphragm side with single side coating Coating is in contact with the side of anode pole piece, positive pole ear be located at single side coating ceramic diaphragm outside, then again with cathode Pole piece is superimposed, and obtains battery core, by the redesign to battery core, is effectively improved the electric discharge specific volume for the first time of Soft Roll lithium-sulfur cell Amount and cycle performance.
Detailed description of the invention
Fig. 1 is the flow chart of step 8) in the present invention；
Fig. 2 is the discharge curve of high specific energy Soft Roll lithium-sulfur cell prepared by embodiment one；
Fig. 3 is the discharge curve of high specific energy Soft Roll lithium-sulfur cell prepared by embodiment two；
Fig. 4 is the discharge curve of high specific energy Soft Roll lithium-sulfur cell prepared by embodiment three；
Fig. 5 is the discharge curve of the high specific energy Soft Roll lithium-sulfur cell of example IV preparation；
Fig. 6 is the discharge curve of high specific energy Soft Roll lithium-sulfur cell prepared by embodiment five.
Specific embodiment
Below with reference to embodiment, the invention will be described in further detail：
Embodiment one
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) ball milling 10h after mixing the porous carbon of 2g with the sublimed sulfur of 1g, obtains mixed-powder；
2) mixed-powder obtained in step 1) is put into hydrothermal reaction kettle, be placed in vacuum drying oven, kept the temperature at 170 DEG C 5h obtains sulphur/porous carbon composite of 3g after the reaction was completed；
3) by sulphur obtained in step 2)/porous carbon mixing material, it is placed in ball grinder, and the Co of 6mg is added3O4Ball milling afterwards 300min obtains the Co of 3.006g3O4Sulphur/porous carbon composite, wherein Co3O4Content be about 2wt%；
4) by Co obtained in step 3)3O4Sulphur/porous carbon composite, by Co3O4Sulphur/porous carbon composite： Super P:PVDF=95:2:3 (mass ratioes) are weighed, by Co3O4After sulphur/porous carbon composite is mixed with Super P Then ball milling 30min mixes the mixture after ball milling with PVDF and NMP, stir 12h under room temperature, keeps slurry mixing equal Even, the solid content of gained slurry is 40%, wherein Co3O4Sulphur/porous carbon composite is 3.006g, and Super P is 0.06g, PVDF is 0.095g, NMP 6.024g；Then slurry is evenly applied on three-dimensional porous aluminium foil with coating machine, then will be coated with The aluminium foil of slurry, which is put in vacuum drying oven, dries 12h at 40 DEG C, after rolling, cutting, obtains pole piece；
5) pole piece obtained in step 4) is carried out to the welding of positive pole ear, then is put in vacuum drying oven and is kept the temperature at 60 DEG C 12h obtains positive plate；
6) three-dimensional porous lithium and three-dimensional foam copper is compound, then it is carried out to cut welding negative lug, obtain cathode pole piece；
7) carbon nanotube of the graphene of 0.5g, 0.5g are mixed with the NMP of PVDF, 0.9g of 0.1g, stirring 12h makes to starch Material is uniformly mixed, and then slurry is evenly applied to the one side of ceramic diaphragm using knife coating, multiple roll-in after drying must have The ceramic diaphragm of single side coating；
8) ceramic diaphragm in step 7) is folded, band coating one side is located at internal layer, and by step 5) just Pole piece is put into the centre of ceramic diaphragm, then bonds the both sides of ceramic diaphragm, and positive pole ear is placed in ceramic diaphragm Outside, the anode pole piece of diaphragm cladding is obtained；
9) step 8) is overlapped with the resulting diaphragm clad anode pole piece of step 6) with cathode pole piece, obtains battery core；
10) it after being packaged battery core with plastic-aluminum packaging film, reinjects 0.3g lithium sulphur electrolyte and encapsulates again, obtain monomer electricity Pond；
11) single battery is subjected to aging process, wherein aging temperature is 65 DEG C, ageing time 12h；
12) battery after aging is subjected to Vacuum Package, high specific energy Soft Roll lithium-sulfur cell is obtained after cutting edge.
Embodiment two
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by the sublimed sulfur ball milling 5.5h of the KS-6 of 6g and 1g, mixed-powder is obtained；
2) mixed-powder obtained in step 1) is put into hydrothermal reaction kettle, be placed in vacuum drying oven, kept the temperature at 145 DEG C 12.5h obtains sulphur/KS-6 composite material of about 7g after reaction；
3) sulphur obtained in step 2)/KS-6 mixing material is placed in ball grinder, the Mg of 1.24g is added0.6Ni0.4After O Ball milling 165min obtains the Mg of about 8.2g0.6Ni0.4O- sulphur/KS-6 composite material, wherein Mg0.6Ni0.4The content of O is about 15wt%；
4) by Mg obtained in step 3)0.6Ni0.4O- sulphur/KS-6 composite material, by Mg0.6Ni0.4O- sulphur/KS-6 composite wood Material:(Super P+ graphene):(PVDF+PTFE)=75:18:7 (mass ratioes) are weighed, by Mg0.6Ni0.4O- sulphur/KS-6 Ball milling 300min after composite material, Super P and graphene mixing, then by the mixture and PVDF, PTFE and NMP after ball milling And deionized water mixes, and stirs 12h under room temperature, is uniformly mixed slurry, the solid content of gained slurry is 55%, wherein Mg0.6Ni0.4O- sulphur/KS-6 composite material is 8.2g, and Super P and graphene are that 0.97g, PVDF and PTFE are 0.385g, NMP 8g, deionized water 0.95g；Then slurry is evenly applied on three-dimensional foam aluminium with coating machine, then will The aluminium foil for being coated with slurry, which is put in vacuum drying oven, dries 10h at 80 DEG C, after rolling, cutting, obtains pole piece；
5) pole piece obtained in step 4) is subjected to positive pole ear welding, then pole piece is put in vacuum drying oven at 60 DEG C and is protected Warm 12h, obtains positive plate；
6) three-dimensional foam lithium and three-dimensional porous copper foil is compound, then it is carried out to cut welding negative lug, obtain negative electrode tab；
7) deionized water of the carbon fiber of KS-6,0.5g of 0.5g, NMP, 0.1g of PVDF, 0.8g of 0.1g are mixed, Stirring 12h is uniformly mixed slurry, then slurry is evenly applied to the one side of ceramic diaphragm using knife coating, after drying repeatedly Roll-in obtains the ceramic diaphragm with single side coating；
8) ceramic diaphragm in step 7) is folded, wherein band coating one side is located at internal layer, and will be in step 5) Positive plate be put into the centre of ceramic diaphragm, then the both sides of ceramic diaphragm are bonded, by positive pole ear be placed in ceramics every Outside film, the positive plate of ceramic diaphragm cladding is obtained；
9) positive plate of step 8) and the resulting ceramic diaphragm cladding of step 6) is overlapped with negative electrode tab, obtains battery core；
10) battery core is packaged with plastic-aluminum packaging film, injection 0.3g lithium sulphur electrolyte encapsulates again, obtains single battery；
11) single battery is subjected to aging process, wherein aging temperature is 65 DEG C, ageing time 12h；
12) single battery after aging is subjected to Vacuum Package, high specific energy Soft Roll lithium-sulfur cell is obtained after cutting edge.
Embodiment three
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by the sublimed sulfur ball milling 1h of graphene-porous carbon of 10g and 1g, mixed-powder is obtained；
2) mixed-powder obtained in step 1) is put into hydrothermal reaction kettle, be placed in vacuum drying oven, kept the temperature at 120 DEG C 20h obtains about 11g sulphur/graphene-porous carbon composite after reaction；
3) sulphur/graphene-porous carbon mixing material obtained in step 2) is placed in ball grinder, adds 2.35g's Mg0.6Ni0.4O and 2.35g Co3O4Ball milling 30min afterwards is obtained
Mg0.6Ni0.4O-Co3O4Sulphur/graphene-porous carbon composite, Mg0.6Ni0.4O and Co3O4Total content be 30wt%；
4) by Mg obtained in step 3)0.6Ni0.4O-Co3O4Sulphur/graphene-porous carbon composite, is pressed Mg0.6Ni0.4O-Co3O4Sulphur/graphene-porous carbon composite:(KS-6+ carbon nanotube):(PVDF+SBR)=55:35:10 (mass ratio) is weighed, by Mg0.6Ni0.4O-Co3O4Sulphur/graphene-porous carbon composite, KS-6 and carbon nanotube ball milling Then 165min mixes the mixture after ball milling with PVDF, SBR and NMP, stir 12h under room temperature, is uniformly mixed slurry, The solid content of gained slurry is 70%, wherein Mg0.6Ni0.4O-Co3O4Sulphur/graphene-porous carbon composite is 15.7g, KS-6 and carbon nanotube are that 5g, PVDF and SBR are 1.425g, NMP 12.235g；Then with coating machine that slurry is uniform It coated on three-dimensional porous aluminium foil, is put in vacuum drying oven and dries 2h at 120 DEG C, after rolling and cutting, obtain pole piece；
5) pole piece obtained in step 4) is subjected to positive pole ear welding, then is put in vacuum drying oven and is kept the temperature at 60 DEG C 12h obtains anode pole piece；
6) it carries out three-dimensional porous copper/lithium metal to cut welding negative lug, obtains cathode pole piece；
7) by the porous carbon of 0.5g, the carbon fiber of 0.5g, 0.05g PTFE, 0.05g CMC and 0.9g NMP mix, stir Mixing 12h is uniformly mixed slurry, then slurry is evenly applied to the one side of ceramic diaphragm using knife coating, multiple roller after drying Pressure, obtains the ceramic diaphragm with single side coating；
8) ceramic diaphragm in step 7) is folded, band coating one side is located at internal layer, and by step 5) just Pole pole piece is put among ceramic diaphragm, then bonds the both sides of ceramic diaphragm, positive pole ear is placed in outside ceramic diaphragm, Obtain the positive plate of ceramic diaphragm cladding；
9) anode pole piece of step 8) and the resulting ceramic diaphragm cladding of step 6) is overlapped with cathode pole piece, is obtained electric Core；
10) battery core is packaged with plastic-aluminum packaging film, reinjects 0.3g lithium sulphur electrolyte and encapsulate again, obtains single battery；
11) single battery is subjected to aging process, wherein aging temperature is 65 DEG C, ageing time 12h；
12) single battery after aging is subjected to Vacuum Package, high specific energy Soft Roll lithium-sulfur cell is obtained after cutting edge.
Example IV
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by the sublimed sulfur ball milling 4h of the graphene of 4g and 1g, mixed-powder is obtained；
2) mixed-powder obtained in step 1) is put into hydrothermal reaction kettle, then is placed in vacuum drying oven and is kept the temperature at 150 DEG C 12h obtains 5g sulphur/graphene mixing material after reaction；
3) sulphur obtained in step 2)/graphene mixing material is placed in ball grinder, the Mg of 0.43g is added0.6Ni0.4O Ball milling 200min afterwards obtains Mg0.6Ni0.4O- sulphur/graphene composite material, Mg0.6Ni0.4The content of O is 8wt%；
4) by Mg obtained in step 3)0.6Ni0.4O- sulphur/graphene composite material, by Mg0.6Ni0.4O- sulphur/graphene is multiple Condensation material:(KS-6+Super P):PVDF=70:25:5 (mass ratioes) are weighed, by Mg0.6Ni0.4O- sulphur/graphene is compound Material, KS-6 and Super P ball milling 180min, then the mixture after ball milling is mixed, stir under room temperature with PVDF and NMP 12h is uniformly mixed slurry, and the solid content of gained slurry is 60%, wherein Mg0.6Ni0.4O- sulphur/graphene composite material is 5.43g, KS-6 and Super P are 0.97g, PVDF 0.4g, NMP 5.18g；Then slurry is uniformly applied using coating machine It is overlying on three-dimensional porous aluminium foil, then the aluminium foil for being coated with slurry is put in vacuum drying oven and dries 12h at 60 DEG C, after cutting, obtain pole Piece；
5) pole piece obtained in step 4) is subjected to positive pole ear welding, then is put in vacuum drying oven and is kept the temperature at 60 DEG C 12h obtains anode pole piece；
6) it carries out three-dimensional foam copper/lithium metal to cut welding negative lug, obtains cathode pole piece；
7) by the carbon nanotube of 0.5g, the carbon fiber of 0.5g, the deionized water of NMP, 0.1g of the PTFE of 0.1g, 0.8g are mixed It closes, stirring 12h is uniformly mixed slurry, and the one side of ceramic diaphragm is then evenly applied to using knife coating, more after drying Secondary roll-in obtains the ceramic diaphragm with single side coating；
8) ceramic diaphragm in step 7) is folded, band coating one side is located at internal layer, and by step 5) just Pole pole piece is put into the centre of ceramic diaphragm, then bonds the both sides of ceramic diaphragm, and positive pole ear is placed in ceramic diaphragm Outside, the anode pole piece of ceramic diaphragm cladding is obtained；
9) step 8) is overlapped with the resulting ceramic diaphragm clad anode piece of step 6) with negative electrode tab, obtains battery core；
10) it after being packaged battery core with plastic-aluminum packaging film, is encapsulated again after injecting the lithium sulphur electrolyte of 0.3g, obtains monomer electricity Pond；
11) single battery is subjected to aging process, wherein aging temperature is 65 DEG C, ageing time 12h；
12) single battery after aging is subjected to Vacuum Package, high specific energy Soft Roll lithium-sulfur cell is obtained after cutting edge.
Embodiment five
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by the sublimed sulfur ball milling 10h of the porous carbon of 8g and 1g, solid mixed-powder is obtained；
2) hybrid solid mixed-powder obtained in step 1) is put into hydrothermal reaction kettle, be placed in vacuum drying oven 150 12h is kept the temperature at DEG C, and sulphur/porous carbon mixing material of 9g is obtained after reaction；
3) sulphur obtained in step 2)/porous carbon mixing material is placed in ball grinder, the Mg of 1.125g is added0.6Ni0.4O With 1.125g Co3O4Ball milling 180min afterwards obtains Mg0.6Ni0.4O-Co3O4Sulphur/graphene composite material, Mg0.6Ni0.4O and Co3O4Total content be 20wt%；
4) by Mg obtained in step 3)0.6Ni0.4O-Co3O4Sulphur/graphene composite material, by Mg0.6Ni0.4O-Co3O4- Sulphur/graphene composite material:(graphene+porous carbon):(PVDF+CMC)=85:15:10 (mass ratioes) are weighed, will Mg0.6Ni0.4O-Co3O4Sulphur/graphene composite material, graphene and porous carbon ball milling 60min, then by the mixture after ball milling It is mixed with PVDF, CMC and NMP, stirs 12h under room temperature, be uniformly mixed slurry, the solid content of gained slurry is 48%, wherein Mg0.6Ni0.4O-Co3O4Sulphur/graphene composite material is 11.25g, and graphene and porous carbon are that 1g, PVDF and CMC are 0.66g, NMP 15.78g；Then slurry is evenly applied on three-dimensional foam aluminium using coating machine, then be put in vacuum drying oven 15h is dried at 100 DEG C, after rolling and cutting, obtains pole piece；
5) pole piece obtained in step 4) is subjected to positive pole ear welding, then pole piece is placed in vacuum drying oven at 120 DEG C Lower heat preservation 12h, obtains positive plate；
6) three-dimensional foam lithium and three-dimensional porous copper foil is compound, then negative lug is welded after cutting to it, obtain cathode Piece；
7) NMP of the carbon fiber of 1g, the PTFE of 0.1g and 0.9g is mixed, stirring 12h is uniformly mixed slurry, then sharp Slurry is evenly applied to the one side of ceramic diaphragm with knife coating, multiple roll-in after drying obtains the ceramics with single side coating Diaphragm；
8) ceramic diaphragm in step 7) is folded, band coating one side is located at internal layer, and by step 5) just Pole piece is put among diaphragm, then bonds the both sides of diaphragm, positive pole ear is placed in outside ceramic diaphragm, obtain ceramics every The positive plate of film cladding；
9) positive plate of step 8) and the resulting ceramic diaphragm cladding of step 6) is overlapped with negative electrode tab, obtains battery core；
10) battery core is packaged with plastic-aluminum packaging film, is encapsulated again after reinjecting the lithium sulphur electrolyte of 0.3g, obtain monomer electricity Pond；
11) single battery is subjected to aging process, wherein aging temperature is 65 DEG C, ageing time 12h；
12) single battery after aging is subjected to Vacuum Package, high specific energy Soft Roll lithium-sulfur cell is obtained after cutting edge.
Embodiment six
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains Metal oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with it is viscous It is coated on plus plate current-collecting body after tying agent A and solvent A mixing, is cut after drying, obtain pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, must has after drying The ceramic diaphragm of single side coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on and has Among the ceramic diaphragm of single side coating, wherein the side of coating and anode pole piece on the ceramic diaphragm side with single side coating Face is in contact, wherein positive pole ear is located at outside the ceramic diaphragm with single side coating, the cathode pole then obtained again with step 6) Piece is superimposed, and obtains battery core；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains monomer electricity Then single battery is carried out pre-arcing and aging process by pond；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, is then cut out Side obtains high specific energy Soft Roll lithium-sulfur cell.
The mass ratio of carbon material and sublimed sulfur is 2 in step 1):1.
The content of metal oxide is 30wt% in metal oxide-sulphur/carbon composite in step 3).
Metal oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is 55 in step 4):2:10；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A consolidating for mixture contain Amount is 40%；
Conductive agent B and binder B mass ratio are 1 in step 7):0.5, conductive agent B, binder B and solvent B mixing after shape The solid content of resulting mixture is 20%.
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and at 170 DEG C At a temperature of insulation reaction 5h, then cooled to room temperature；
The time of ball milling is 30min in step 3)；
Drying in step 4) uses vacuum drying mode, and drying temperature is 120 DEG C, drying time 2h；
The time of ball milling is 30min in step 4).
Carbon material is KS-6.
Metal oxide is Mg0.6Ni0.4O。
Conductive agent A is Super P；
Conductive agent B is Super P.
Binder A is PVDF；
Binder B is PVDF；
Solvent A is NMP；
Solvent B is NMP.
Plus plate current-collecting body is three-dimensional porous aluminium foil；
Negative current collector is three-dimensional porous copper foil；
Cathode of lithium is three-dimensional foam lithium.
Embodiment seven
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains Metal oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with it is viscous It is coated on plus plate current-collecting body after tying agent A and solvent A mixing, is cut after drying, obtain pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, must has after drying The ceramic diaphragm of single side coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on and has Among the ceramic diaphragm of single side coating, wherein the side of coating and anode pole piece on the ceramic diaphragm side with single side coating Face is in contact, wherein positive pole ear is located at outside the ceramic diaphragm with single side coating, the cathode pole then obtained again with step 6) Piece is superimposed, and obtains battery core；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains monomer electricity Then single battery is carried out pre-arcing and aging process by pond；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, is then cut out Side obtains high specific energy Soft Roll lithium-sulfur cell.
The mass ratio of carbon material and sublimed sulfur is 10 in step 1):1.
The content of metal oxide is 2wt% in metal oxide-sulphur/carbon composite in step 3).
Metal oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is 95 in step 4):35:3；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A consolidating for mixture contain Amount is 70%；
Conductive agent B and binder B mass ratio are 1 in step 7):2, it is formed after conductive agent B, binder B and solvent B mixing The solid content of mixture is 40%.
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and at 120 DEG C At a temperature of insulation reaction 20h, then cooled to room temperature；
The time of ball milling is 300min in step 3)；
Drying in step 4) uses vacuum drying mode, and drying temperature is 40 DEG C, drying time 12h；
The time of ball milling is 300min in step 4).
Carbon material is graphene.
Metal oxide is Co3O4。
Conductive agent A is KS-6；
Conductive agent B is KS-6.
Binder A is PTFE；
Binder B is PTFE；
Solvent A is deionized water；
Solvent B is deionized water.
Plus plate current-collecting body is three-dimensional foam aluminium；
Negative current collector is three-dimensional foam copper；
Cathode of lithium is three-dimensional porous lithium.
Embodiment eight
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains Metal oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with it is viscous It is coated on plus plate current-collecting body after tying agent A and solvent A mixing, is cut after drying, obtain pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, must has after drying The ceramic diaphragm of single side coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on and has Among the ceramic diaphragm of single side coating, wherein the side of coating and anode pole piece on the ceramic diaphragm side with single side coating Face is in contact, wherein positive pole ear is located at outside the ceramic diaphragm with single side coating, the cathode pole then obtained again with step 6) Piece is superimposed, and obtains battery core；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains monomer electricity Then single battery is carried out pre-arcing and aging process by pond；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, is then cut out Side obtains high specific energy Soft Roll lithium-sulfur cell.
The mass ratio of carbon material and sublimed sulfur is 8 in step 1):1.
The content of metal oxide is 20wt% in metal oxide-sulphur/carbon composite in step 3).
Metal oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is 60 in step 4):20:6；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A consolidating for mixture contain Amount is 60%；
Conductive agent B and binder B mass ratio are 1 in step 7):1, it is formed after conductive agent B, binder B and solvent B mixing The solid content of mixture is 30%.
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and at 150 DEG C At a temperature of insulation reaction 15h, then cooled to room temperature；
The time of ball milling is 200min in step 3)；
Drying in step 4) uses vacuum drying mode, and drying temperature is 100 DEG C, drying time 8h；
The time of ball milling is 100min in step 4).
Carbon material is carbon nanotube.
Metal oxide is Mg0.6Ni0.4O and Co3O4The mixture mixed in any proportion.
Conductive agent A is graphene；
Conductive agent B is graphene.
Binder A is PEO；
Binder B is PEO；
The mixture that solvent A is NMP and deionized water mixes in any proportion；
The mixture that solvent B is NMP and deionized water mixes in any proportion.
Plus plate current-collecting body is three-dimensional porous aluminium foil；
Negative current collector is three-dimensional porous copper foil；
Cathode of lithium is three-dimensional foam copper/lithium metal.
Embodiment nine
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains Metal oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with it is viscous It is coated on plus plate current-collecting body after tying agent A and solvent A mixing, is cut after drying, obtain pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, must has after drying The ceramic diaphragm of single side coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on and has Among the ceramic diaphragm of single side coating, wherein the side of coating and anode pole piece on the ceramic diaphragm side with single side coating Face is in contact, wherein positive pole ear is located at outside the ceramic diaphragm with single side coating, the cathode pole then obtained again with step 6) Piece is superimposed, and obtains battery core；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains monomer electricity Then single battery is carried out pre-arcing and aging process by pond；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, is then cut out Side obtains high specific energy Soft Roll lithium-sulfur cell.
The mass ratio of carbon material and sublimed sulfur is 3 in step 1):1.
The content of metal oxide is 5wt% in metal oxide-sulphur/carbon composite in step 3).
Metal oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is 40 in step 4):10:5；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A consolidating for mixture contain Amount is 50%；
Conductive agent B and binder B mass ratio are 1 in step 7):0.8, conductive agent B, binder B and solvent B mixing after shape The solid content of resulting mixture is 25%.
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and at 130 DEG C At a temperature of insulation reaction 11h, then cooled to room temperature；
The time of ball milling is 50min in step 3)；
Drying in step 4) uses vacuum drying mode, and drying temperature is 60 DEG C, drying time 4h；
The time of ball milling is 60min in step 4).
Carbon material is carbon fiber.
Metal oxide is Mg0.6Ni0.4O。
Conductive agent A is carbon nanotube；
Conductive agent B is carbon nanotube.
Binder A is SBR；
Binder B is SBR；
Solvent A is deionized water；
Solvent B is deionized water.
Plus plate current-collecting body is three-dimensional foam aluminium；
Negative current collector is three-dimensional foam copper；
Cathode of lithium is three-dimensional porous lithium.
Embodiment ten
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains Metal oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with it is viscous It is coated on plus plate current-collecting body after tying agent A and solvent A mixing, is cut after drying, obtain pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, must has after drying The ceramic diaphragm of single side coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on and has Among the ceramic diaphragm of single side coating, wherein the side of coating and anode pole piece on the ceramic diaphragm side with single side coating Face is in contact, wherein positive pole ear is located at outside the ceramic diaphragm with single side coating, the cathode pole then obtained again with step 6) Piece is superimposed, and obtains battery core；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains monomer electricity Then single battery is carried out pre-arcing and aging process by pond；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, is then cut out Side obtains high specific energy Soft Roll lithium-sulfur cell.
The mass ratio of carbon material and sublimed sulfur is 9 in step 1):1.
The content of metal oxide is 25wt% in metal oxide-sulphur/carbon composite in step 3).
Metal oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is 90 in step 4):30:8；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A consolidating for mixture contain Amount is 60%；
Conductive agent B and binder B mass ratio are 1 in step 7):1.5, conductive agent B, binder B and solvent B mixing after shape The solid content of resulting mixture is 35%.
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and at 160 DEG C At a temperature of insulation reaction 18h, then cooled to room temperature；
The time of ball milling is 280min in step 3)；
Drying in step 4) uses vacuum drying mode, and 100 DEG C of drying temperature, drying time 11h；
The time of ball milling is 280min in step 4).
Carbon material is porous carbon.
Metal oxide is Co3O4。
Conductive agent A is carbon fiber；
Conductive agent B is carbon fiber.
Binder A is CMC；
Binder B is CMC；
Solvent A is NMP；
Solvent B is NMP.
Plus plate current-collecting body is three-dimensional porous aluminium foil；
Negative current collector is three-dimensional porous copper foil；
Cathode of lithium is three-dimensional porous copper/lithium metal.
Embodiment 11
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains Metal oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with it is viscous It is coated on plus plate current-collecting body after tying agent A and solvent A mixing, is cut after drying, obtain pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, must has after drying The ceramic diaphragm of single side coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on and has Among the ceramic diaphragm of single side coating, wherein the side of coating and anode pole piece on the ceramic diaphragm side with single side coating Face is in contact, wherein positive pole ear is located at outside the ceramic diaphragm with single side coating, the cathode pole then obtained again with step 6) Piece is superimposed, and obtains battery core；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains monomer electricity Then single battery is carried out pre-arcing and aging process by pond；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, is then cut out Side obtains high specific energy Soft Roll lithium-sulfur cell.
The mass ratio of carbon material and sublimed sulfur is 3 in step 1):1.
The content of metal oxide is 15wt% in metal oxide-sulphur/carbon composite in step 3).
Metal oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is 70 in step 4):18:6；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A consolidating for mixture contain Amount is 45%；
Conductive agent B and binder B mass ratio are 1 in step 7):1.2, conductive agent B, binder B and solvent B mixing after shape The solid content of resulting mixture is 24%.
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and at 130 DEG C At a temperature of insulation reaction 9h, then cooled to room temperature；
The time of ball milling is 80min in step 3)；
Drying in step 4) uses vacuum drying mode, and drying temperature is 60 DEG C, drying time 9h；
The time of ball milling is 45min in step 4).
Carbon material is the mixture that carbon fiber and porous carbon arbitrary proportion mix.
Metal oxide is Mg0.6Ni0.4O。
Conductive agent A is porous carbon；
Conductive agent B is porous carbon.
Binder A is the mixture that SBR and CMC are mixed in any proportion；
Binder B is the mixture that SBR and CMC are mixed in any proportion；
Solvent A is deionized water；
Solvent B is deionized water.
Plus plate current-collecting body is three-dimensional foam aluminium；
Negative current collector is three-dimensional foam copper；
Cathode of lithium is three-dimensional foam lithium.
Embodiment 12
The production method of high specific energy Soft Roll lithium-sulfur cell of the present invention includes the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains Metal oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with it is viscous It is coated on plus plate current-collecting body after tying agent A and solvent A mixing, is cut after drying, obtain pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, must has after drying The ceramic diaphragm of single side coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on and has Among the ceramic diaphragm of single side coating, wherein the side of coating and anode pole piece on the ceramic diaphragm side with single side coating Face is in contact, wherein positive pole ear is located at outside the ceramic diaphragm with single side coating, the cathode pole then obtained again with step 6) Piece is superimposed, and obtains battery core；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains monomer electricity Then single battery is carried out pre-arcing and aging process by pond；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, is then cut out Side obtains high specific energy Soft Roll lithium-sulfur cell.
The mass ratio of carbon material and sublimed sulfur is 3 in step 1):1.
The content of metal oxide is 6wt% in metal oxide-sulphur/carbon composite in step 3).
Metal oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is 75 in step 4):15:6；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A consolidating for mixture contain Amount is 60%；
Conductive agent B and binder B mass ratio are 1 in step 7):0.6, conductive agent B, binder B and solvent B mixing after shape The solid content of resulting mixture is 22%.
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and 120~ Insulation reaction 6h at a temperature of 170 DEG C, then cooled to room temperature；
The time of ball milling is 250min in step 3)；
Drying in step 4) uses vacuum drying mode, and drying temperature is 110 DEG C, drying time 8h；
The time of ball milling is 130min in step 4).
Carbon material is the mixture that KS-6, graphene, carbon nanotube, carbon fiber and porous carbon arbitrary proportion mix.
Metal oxide is Mg0.6Ni0.4O and Co3O4The mixture mixed in any proportion.
Conductive agent A is what Super P, KS-6, graphene, carbon nanotube, carbon fiber and porous carbon mixed in any proportion Mixture；
Conductive agent B is what Super P, KS-6, graphene, carbon nanotube, carbon fiber and porous carbon mixed in any proportion Mixture.
Binder A is the mixture that PVDF, PTFE, PEO, SBR and CMC are mixed in any proportion；
Binder B is the mixture that PVDF, PTFE, PEO, SBR and CMC are mixed in any proportion；
Solvent A is NMP；
Solvent B is NMP.
Plus plate current-collecting body is three-dimensional porous aluminium foil；
Negative current collector is three-dimensional porous copper foil；
Cathode of lithium is three-dimensional porous lithium.
By optimizing selection to carbon material, good sheet or classification cavernous structure are made it have, can be formed The conductive network of high speed can make electrically realized quick transmission；In addition, by the coating by graphene and carbon nanotube building, Its duct or aperture can be regulated and controled by the selection of material, and lesser aperture will be helpful to increase the diffusion mobility of more lithium sulfides Resistance.
Using three-dimensional porous copper foil or three-dimensional foam copper as the negative current collector of battery, negative electrode active material both may act as Carrier, and may act as collection and the transmission body of cathode electron stream, it is compound with lithium metal, or pass through electro-deposition for lithium metal It deposits to three-dimensional porous copper, on three-dimensional foam copper, obtains three-dimensional porous copper/lithium metal or three-dimensional foam copper/lithium metal, it can be effective The utilization rate for improving lithium, to effectively improve the whole volume of lithium-sulfur cell.

Claims (10)

1. a kind of production method of high specific energy Soft Roll lithium-sulfur cell, which is characterized in that include the following steps：
1) by carbon material and sublimed sulfur mixing and ball milling, mixed-powder is obtained；
2) mixed-powder for obtaining step 1) is put into hydrothermal reaction kettle and reacts, and obtains sulphur/carbon composite；
3) sulphur/carbon composite for obtaining step 2) is placed in ball grinder, is added metal oxide and is carried out ball milling, obtains metal Oxide-sulphur/carbon composite；
4) metal oxide-sulphur for obtaining conductive agent A and step 3)/carbon composite carries out ball milling, then again with binder A And be coated on plus plate current-collecting body after solvent A mixing, it is cut after drying, obtains pole piece；
5) pole piece for obtaining step 4) carries out the welding of positive pole ear, obtains anode pole piece；
6) by cathode of lithium and negative pole currect collecting bluk recombination, negative lug is welded after cutting, obtains cathode pole piece；
7) conductive agent B, binder B and solvent B are mixed, is then coated in the side of ceramic diaphragm, there must be single side after drying The ceramic diaphragm of coating；
8) ceramic diaphragm with single side coating is folded, then the anode pole piece that step 5) is obtained is held on single side Among the ceramic diaphragm of coating, wherein the side phase of coating and anode pole piece on the ceramic diaphragm side with single side coating Contact, positive pole ear are located at outside the ceramic diaphragm with single side coating, and the cathode pole piece then obtained again with step 6) is superimposed upon Together, battery core is obtained；
9) battery core for obtaining step 8) carries out closedtop and side seal encapsulation at tab by plastic-aluminum packaging film, obtains single battery, so Single battery is subjected to pre-arcing and aging process afterwards；
10) single battery after the pre-arcing and aging process that obtain step 9) carries out Vacuum Package, then carries out cutting edge, obtains High specific energy Soft Roll lithium-sulfur cell.
2. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that carbon materials in step 1) The mass ratio of material and sublimed sulfur is (2~10):1.
3. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that metal in step 3) The content of metal oxide is (2~30) wt% in oxide-sulphur/carbon composite.
4. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that metal in step 4) Oxide-sulphur/carbon composite, conductive agent A and binder A mass ratio is (95~55):(2~35):(3~10)；
Metal oxide-sulphur/carbon composite in step 4), conductive agent A, binder A and solvent A the solid content of mixture be (40~70) %；
Conductive agent B and binder B mass ratio are 1 in step 7):Shape after (0.5~2), conductive agent B, binder B and solvent B mixing At mixture solid content be 20%~40%.
5. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that
The concrete operations of step 2) are：The mixed-powder that step 1) is obtained is put into hydrothermal reaction kettle, and in (120~170) Insulation reaction (5~20) h at a temperature of DEG C, then cooled to room temperature；
The time of ball milling is (30~300) min in step 3)；
Drying in step 4) uses vacuum drying mode, and drying temperature is (40-120) DEG C, and drying time is (2-12) h；
The time of ball milling is (30~300) min in step 4).
6. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that carbon material KS- 6, one of graphene, carbon nanotube, carbon fiber and porous carbon or a variety of mixtures mixed in any proportion.
7. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that metal oxide is Mg0.6Ni0.4O and Co3O4One or both of the mixture that mixes in any proportion.
8. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that conductive agent A is One of Super P, KS-6, graphene, carbon nanotube, carbon fiber and porous carbon or a variety of mixing mixed in any proportion Object；
Conductive agent B is one of Super P, KS-6, graphene, carbon nanotube, carbon fiber and porous carbon or a variety of by any The mixture of ratio mixing.
9. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that
Binder A is one of PVDF, PTFE, PEO, SBR and CMC or a variety of mixtures mixed in any proportion；
Binder B is one of PVDF, PTFE, PEO, SBR and CMC or a variety of mixtures mixed in any proportion；
Solvent A is the mixture that one or both of NMP and deionized water are mixed in any proportion；
Solvent B is the mixture that one or both of NMP and deionized water are mixed in any proportion.
10. the production method of high specific energy Soft Roll lithium-sulfur cell according to claim 1, which is characterized in that
Plus plate current-collecting body is three-dimensional porous aluminium foil or three-dimensional foam aluminium；
Negative current collector is three-dimensional porous copper foil or three-dimensional foam copper；
Cathode of lithium is three-dimensional porous lithium, three-dimensional foam lithium, three-dimensional porous copper/lithium metal or three-dimensional foam copper/lithium metal.
CN201810670455.2A 2018-06-22 2018-06-22 A kind of production method of high specific energy Soft Roll lithium-sulfur cell Pending CN108899584A (en)

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Application publication date: 20181127