CN109686981A - A kind of compound binding agent and preparation method thereof applied to lithium-sulfur cell - Google Patents
A kind of compound binding agent and preparation method thereof applied to lithium-sulfur cell Download PDFInfo
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- CN109686981A CN109686981A CN201811592627.5A CN201811592627A CN109686981A CN 109686981 A CN109686981 A CN 109686981A CN 201811592627 A CN201811592627 A CN 201811592627A CN 109686981 A CN109686981 A CN 109686981A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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Abstract
The compound binding agent and preparation method thereof that the present invention relates to a kind of applied to lithium-sulfur cell, belongs to lithium-sulfur cell technical field.Compound binding agent applied to lithium-sulfur cell of the invention, including transition metal organic coordination compounds and binder；The transition metal organic coordination compounds are made by organic ligand and soluble transition metal reactant salt.Transition metal organic coordination compounds in compound binding agent applied to lithium-sulfur cell of the invention are in pole piece drying course by being self-assembly of the hybrid inorganic-organic materials with molecule inner pore, electrolyte is enabled to be impregnated with pole piece well by hole, so as to improve the ionic conductivity of pole piece, in the case where pole piece active layer is thicker, guarantee that ionic conduction can reach entire active layer；The metallic element in hybrid inorganic-organic materials being formed simultaneously has catalytic action to the chemical reaction of sulfide, is able to ascend the energy density of battery.
Description
Technical field
The compound binding agent and preparation method thereof that the present invention relates to a kind of applied to lithium-sulfur cell, belongs to lithium-sulfur cell technology
Field.
Background technique
The theoretical specific capacity of sulphur is up to 1675mAh/g, much higher than the positive electrode (reason of ternary material of current business application
By specific capacity 280mAh/g), lithium-sulfur cell is widely studied as the lithium ion battery of a new generation.In order to realize lithium-sulfur cell
Commercial applications, mass energy density need >=350Wh/kg (at present the lithium ion battery energy density of business application~
220Wh/kg), the realization of this target, it is necessary to which high with pole piece carries sulfur content (>=4mg/cm2) premised on, and report at present
Height ratio capacity (>=1300mAh/g) lithium-sulfur cell, pole piece carry the lower (≤2mg/cm of sulfur content2), the pole required with business application
Piece carries sulfur content at a distance of larger, therefore, realizes that pole piece height carries the height ratio capacity under sulfur content and plays and has important practical application value.
Currently, being concentrated mainly on positive electrode synthesis aspect for improving pole piece load sulphur quantifier elimination, such as: the different of sulphur are carried
Body material, pattern/structure control of composite particles, element doping etc., although making remarkable progress, due to it is expensive,
Or the reasons such as process complexity or synthesis condition harshness, do not have practical application value.And, cost simple for synthesis condition
Low common mesoporous carbon/sulphur composite material carries sulfur content (>=4mg/cm in pole piece height2) under high capacity play, be rarely reported.This
It is primarily due to, sulphur and reaction product Li2S/Li2S2Electric conductivity is poor, when pole piece height carries sulfur content, using common carbon materials
Material, influence of this intrinsic defect to pole piece electrical property are more obvious.Since the conductivity of electronics on pole piece is low, internal resistance is bigger than normal,
Make the voltage of the 2nd discharge voltage plateau (~2.05V) that rapid drawdown occur, causes capacity relatively low.
For the electric conductivity for improving sulfur granules, sulphur and the compound of conducting polymer are widely studied.Polythiophene, gathers polyaniline
Close the Chinese invention patent Shen that object 3,4-rthylene dioxythiophene etc. and sulphur is compound and application publication number is 106356513 A of CN
Please in report sandwich structure polyaniline/sulphur composite material, all reached the specific capacity of 800mAh/g or more, but this high score
Son/sulphur composite material sulphur ratio only has 50% or so (mesoporous carbon/sulphur composite material sulphur ratio is up to 70% or so), unfavorable
In the high load sulfur content for realizing pole piece.It is led in the Chinese invention patent application that application publication number is CN105655593A using macromolecule
Electric binder replaces traditional binder (PVDF, CMC/SBR, LA132 etc.), by reduction internal resistance, improves battery specific capacity,
But in the case where pole piece height carries sulfur content, specific capacity is still lower.Although this is because pole piece electronics conduction improved, pole piece from
Sub- conductibility does not change, and in the case where pole piece height carries sulfur content, pole piece is thicker, and ionic conduction cannot go deep into the bottom of pole piece, causes electricity
Tankage is lower.
Summary of the invention
The object of the present invention is to provide a kind of compound binding agents applied to lithium-sulfur cell, can promote ion in pole piece
Conduction.
The present invention also provides a kind of preparation methods of the compound binding agent applied to lithium-sulfur cell of simple process.
In order to achieve the goal above, technical solution used by the compound binding agent applied to lithium-sulfur cell of the invention
It is:
A kind of compound binding agent applied to lithium-sulfur cell, including transition metal organic coordination compounds and binder；Institute
Transition metal organic coordination compounds are stated to be made by organic ligand and soluble transition metal reactant salt；It is the binder, organic
The mass ratio of ligand and soluble transition metal salt is 1.5~20:0.5~10:0.25~2.5.
Compound binding agent applied to lithium-sulfur cell of the invention is matched containing organic ligand and the life of soluble transition metal salt
The transition metal organic coordination compounds that position reaction generates are self-assembly of as the solvent evaporates in pole piece drying course
Hybrid inorganic-organic materials with molecule inner pore, electrolyte can be impregnated with pole piece by this hole well, to change
The ionic conductivity of kind pole piece guarantees that ionic conduction can reach entire active layer in the case where pole piece active layer is thicker, from
And improve the first discharge specific capacity and cyclic specific capacity of lithium-sulfur cell；The gold in hybrid inorganic-organic materials being formed simultaneously
Belonging to chemical reaction of the element to sulfide, there are also certain catalytic action, can further promote the energy density of battery.
The present invention is not particularly limited the Binder Composition in the compound binding agent for being applied to lithium-sulfur cell, conventional use
It can be used in the binder such as Kynoar (PVDF) of lithium-sulphur cell positive electrode, sodium carboxymethylcellulose (CMC) etc..In order to subtract
Influence of the small conventional binders to electronics and ion in pole piece, it is preferred that the binder is conductive polymer material.
Preferably, the conductive polymer material is selected from polyaniline, polypyrrole, polythiophene, poly- furans, polyselenophenes, poly- pair
At least one of sub- benzene, polyphenylene sulfide.Above-mentioned several conductive polymer materials not only have good conductive property, and have simultaneously
There is higher caking property.
When using conductive polymer material as binder, prepared in order to avoid being applied to the compound binding agent of lithium-sulfur cell
Chelatropic reaction occurs between conductive polymer material and metal salt in the process, influences the generation in hybrid inorganic-organic materials gap,
Bi-component is made in the compound binding agent for being applied to lithium-sulfur cell to store respectively.Preferably, the answering applied to lithium-sulfur cell
Closing binder includes component A and component B；The component A includes the transition metal organic coordination compounds and solvent A；It is described
Component B includes the conductive polymer material and solvent B.The compound binding agent use process applied to lithium-sulfur cell of bi-component
Middle to mix component A with component B, with conductive polymer material chelatropic reaction occurs for soluble transition metal salt again at this time, this is right
It is that one kind is metal-doped for conductive polymer material, the electric conductivity of conductive polymer material can be further increased.
Technical solution used by the preparation method of compound binding agent applied to lithium-sulfur cell of the invention are as follows:
A kind of preparation method of the compound binding agent applied to lithium-sulfur cell, comprising: by organic ligand and soluble transition
Metal salt is uniformly mixed in solvent A, obtains component A；Binder and solvent B are uniformly mixed, component B is obtained；The bonding
The mass ratio of agent, organic ligand and soluble transition metal salt is 1.5~20:0.5~10:0.25~2.5.
The preparation method of compound binding agent applied to lithium-sulfur cell of the invention, simple process are easy to promote and utilize.
Preferably, the binder is conductive polymer material.
Preferably, the conductive polymer material is selected from polyaniline, polypyrrole, polythiophene, poly- furans, polyselenophenes, poly- pair
At least one of sub- benzene, polyphenylene sulfide.
Detailed description of the invention
Fig. 1 is capacitance-voltage performance map when Soft Roll lithium-sulfur cell (2Ah) recycles 100 times in experimental example 1 of the invention；
Fig. 2 is cycle-index-specific capacity performance map of button cell A1 obtained in experimental example 2 of the invention；
Fig. 3 is cycle-index-specific capacity performance map of button cell A2 obtained in experimental example 2 of the invention；
Fig. 4 is cycle-index-specific capacity performance map of button cell A3 obtained in experimental example 2 of the invention.
Specific embodiment
Compound binding agent provided by the invention applied to lithium-sulfur cell, including transition metal organic coordination compounds and viscous
Tie agent；The transition metal organic coordination compounds are made by organic ligand and soluble transition metal reactant salt；The bonding
The mass ratio of agent, organic ligand and soluble transition metal salt is 1.5~20:0.5~10:0.25~2.5.
Binder can choose conventional binder.As to be applied to lithium-sulfur cell a kind of modification of compound binding agent,
Binder selects conductive polymer material.
Preferably, the compound binding agent applied to lithium-sulfur cell of the invention is used for the anode of lithium-sulfur cell.Using this hair
The positive plate of the bright compound binding agent applied to lithium-sulfur cell can provide in charge and discharge process for ion transmission more
Channel greatly improves the energy density of lithium-sulfur cell so that pole piece has good ionic conductivity；It is particularly applied to lithium sulphur
It is also avoided that in the compound binding agent of battery using conductive polymer material as binder and electronics is conducted using conventional binders
Influence, improve the electron conduction of pole piece.
As the further modification to the compound binding agent for being applied to lithium-sulfur cell, conductive polymer material is selected from polyphenyl
At least one of amine, polypyrrole, polythiophene, poly- furans, polyselenophenes, poly, polyphenylene sulfide.
Organic ligand can be selected from terephthalic acid (TPA), M-phthalic acid, trimesic acid, cyclodextrin, imidazoles, 4- methyl miaow
Azoles, 1- vinyl imidazole, N, N '-carbonyl dimidazoles, 2-methyl-5-vinylpyrine, 2- acetylpyridine, L-Trp, 1,
At least one of 2- bis- (4- pyridyl group) ethylene, bipyridyl.
Soluble transition metal salt can be selected from least one of soluble cobalt salt, zinc salt, chromic salts, nickel salt.It is solvable
Property cobalt salt is preferably cobalt chloride, at least one of the preferred zinc nitrate of soluble zinc salt, zinc acetate, and soluble chromic salts is preferred
Chromic nitrate, the preferred nickel acetate of soluble nickel salt.
Compound binding agent applied to lithium-sulfur cell further includes solvent.The solvent includes water and organic solvent；It is described to have
Solvent is selected from ethyl alcohol, n-butanol, acetone, tetrahydrofuran, dimethyl sulfoxide, toluene, ethylene glycol, propylene glycol monomethyl ether, dimethyl
Formamide, dimethyl acetamide, ethyl acetate, dibutyl phthalate, chloroform, at least one in N-Methyl pyrrolidone
Kind.
It is described applied to the compound viscous of lithium-sulfur cell as a kind of modification to the compound binding agent for being applied to lithium-sulfur cell
Tying agent includes component A and component B；The component A includes the transition metal organic coordination compounds and solvent A；The component B
Including the conductive polymer material and solvent B.The preparation method of the component A include: by the organic ligand and it is described can
Dissolubility transition metal salt mixed in solvent A to get.This is applied to the compound binding agent of lithium-sulfur cell in use, realizing component A
With the mixing of component B；Component A and component B can also be mixed using preceding.
Preferably, the mass ratio of component A and component B are 1~1.1:1.It is organic for reacting transition metal in generation component A
The organic ligand of complex and the mass ratio of solvent A are 1:9~190.The matter of conducting polymer material and solvent B in component B
Amount is than being 1:4~66.
The solvent A includes being made of water and organic solvent；The organic solvent is selected from tetrahydrofuran, ethyl alcohol, dimethyl
At least one of acetamide.The volume ratio of water and organic solvent is 1~4:1 in solvent A.
The solvent B includes organic solvent, the organic solvent be selected from dimethylformamide, n-butanol, dimethyl sulfoxide,
At least one of chloroform, tetrahydrofuran, N-Methyl pyrrolidone.The solvent B further includes water, the volume of organic solvent and water
Than for 0.65~3:1.
The preparation method of compound binding agent provided by the invention applied to lithium-sulfur cell, comprising: by organic ligand and can
Dissolubility transition metal salt is uniformly mixed in solvent A, obtains component A；Binder and solvent B are uniformly mixed, component B is obtained；
The mass ratio of the binder, organic ligand and soluble transition metal salt is 1.5~20:0.5~10:0.25~2.5.
In the preparation method of the above-mentioned compound binding agent applied to lithium-sulfur cell, organic ligand can be selected from terephthaldehyde
Acid, M-phthalic acid, trimesic acid, cyclodextrin, imidazoles, 4-methylimidazole, 1- vinyl imidazole, N, N '-carbonyl dimidazoles,
2-methyl-5-vinylpyrine, 2- acetylpyridine, L-Trp, 1,2- bis- (4- pyridyl group) ethylene, in bipyridyl at least
It is a kind of.Soluble transition metal salt can be selected from least one of soluble cobalt salt, zinc salt, chromic salts, nickel salt.Soluble cobalt
Salt is preferably cobalt chloride, at least one of the preferred zinc nitrate of soluble zinc salt, zinc acetate, the preferred nitric acid of soluble chromic salts
Chromium, the preferred nickel acetate of soluble nickel salt.
In the preparation method of the above-mentioned compound binding agent applied to lithium-sulfur cell, it is preferred that the quality of component A and component B
Than for 1~1.1:1.The mass ratio of organic ligand and solvent A is 1:9~190.The matter of conducting polymer material and solvent B in component B
Amount is than being 1:4~66.
Above-mentioned system is applied in the Preparation Method of the compound binding agent of lithium-sulfur cell, it is preferred that the solvent A include by water and
Organic solvent composition；The organic solvent be selected from tetrahydrofuran, ethyl alcohol, dimethyl acetamide at least one.In solvent A water and
The volume ratio of organic solvent is 1~4:1.
In the preparation method of the above-mentioned compound binding agent applied to lithium-sulfur cell, it is preferred that the solvent B includes organic molten
Agent, the organic solvent are selected from dimethylformamide, n-butanol, dimethyl sulfoxide, chloroform, tetrahydrofuran, N- crassitude
At least one of ketone.The solvent B further includes water, and the volume ratio of organic solvent and water is 0.65~3:1.
The present invention also provides a kind of preparation methods of lithium-sulfur cell positive plate, comprising the following steps: sulfenyl is compound
Anode sizing agent is made in material, conductive agent and the compound binding agent applied to lithium-sulfur cell；Then anode sizing agent is coated in
On collector, then be dried to get.
In the preparation method of above-mentioned lithium-sulfur cell positive plate, used sulfenyl composite material includes sulphur and for loading
The carrier of sulphur；The carrier be mesoporous carbon, CNTs, graphene, carbon nanosheet, SP, KS-6, acetylene black, in Ketjen black at least
It is a kind of.The mass percentage of sulphur is 60~75%, preferably 68~70% in the sulfenyl composite material material.
Dry temperature is preferably 45~80 DEG C.Preferably 8~12h of dry time.
Below in conjunction with specific embodiment, further description of the technical solution of the present invention.
In following embodiment, Examples 1 to 8 is the embodiment of the compound binding agent applied to lithium-sulfur cell, and embodiment 9 is
The embodiment of the preparation method of compound binding agent for lithium-sulfur cell, embodiment 10~17 are the system of lithium-sulfur cell positive plate
Preparation Method.
Embodiment 1
The compound binding agent applied to lithium-sulfur cell of the present embodiment, is made of component A and component B, component A and component B
Mass ratio be 1:1；
Component A includes transition metal organic coordination compounds and solvent A；Transition metal organic coordination compounds are matched by organic
Body, soluble transition metal reaction are made；The mass ratio of organic ligand, soluble transition metal salt and solvent A is 5:0.5:
94.5, organic ligand is M-phthalic acid, and soluble transition metal salt is cobalt chloride；Solvent A is the mixing of water and tetrahydrofuran
The volume ratio of liquid, water and tetrahydrofuran is 2:1；
Component B is made of conductive polymer material (i.e. binder) and solvent B, the matter of conductive polymer material and solvent B
For amount than being 5:95, conductive polymer material is polyaniline；Solvent B be water, dimethylformamide and n-butanol mixed liquor, water,
The volume ratio of dimethylformamide and n-butanol is 2:2:1.
Embodiment 2
The compound binding agent applied to lithium-sulfur cell of the present embodiment, is made of component A and component B, component A and component B
Mass ratio be 1:1；
Component A includes transition metal organic coordination compounds and solvent A；Transition metal organic coordination compounds are matched by organic
Body, soluble transition metal reaction are made；The mass ratio of organic ligand, soluble transition metal salt and solvent A is 8:0.25:
91.75, organic ligand is cyclodextrin, and soluble transition metal salt is zinc acetate；Solvent A be water and ethyl alcohol mixed liquor, water and
The volume ratio of ethyl alcohol is 1:1；
Component B is made of conductive polymer material (i.e. binder) and solvent B, the matter of conductive polymer material and solvent B
For amount than being 7:93, conductive polymer material is polyphenylene sulfide；Solvent B is the mixed liquor of dimethyl sulfoxide and chloroform, and dimethyl is sub-
The volume ratio of sulfone and chloroform is 10:1.
Embodiment 3
The compound binding agent applied to lithium-sulfur cell of the present embodiment, is made of component A and component B, component A and component B
Mass ratio be 1:1；
Component A includes transition metal organic coordination compounds and solvent A；Transition metal organic coordination compounds are matched by organic
Body, soluble transition metal reaction are made；The mass ratio of organic ligand, soluble transition metal salt and solvent A is 5:0.5:
94.5, organic ligand is 1- vinyl imidazole, and soluble transition metal salt is nickel acetate；Solvent A be water, dimethyl acetamide and
The mixed liquor of ethyl alcohol, the volume ratio of water, dimethyl acetamide and ethyl alcohol are 6:3:1；
Component B is made of conductive polymer material (i.e. binder) and solvent B, the matter of conductive polymer material and solvent B
For amount than being 5:95, conductive polymer material is polythiophene；Solvent B is the mixed liquor of water and tetrahydrofuran, water and tetrahydrofuran
Volume ratio is 3:1.
Embodiment 4
The compound binding agent applied to lithium-sulfur cell of the present embodiment, is made of component A and component B；
Component A includes transition metal organic coordination compounds and solvent A；Transition metal organic coordination compounds are matched by organic
Body, soluble transition metal reaction are made；The mass ratio of organic ligand, soluble transition metal salt and solvent A is 10:2.5:
94.5, organic ligand is 2-methyl-5-vinylpyrine, and soluble transition metal salt is chromic nitrate；Solvent A is water, dimethyl
The mixed liquor of acetamide and ethyl alcohol, the volume ratio of water, dimethyl acetamide and ethyl alcohol are 2:1:1；
Component B is made of conductive polymer material (i.e. binder) and solvent B, the matter of conductive polymer material and solvent B
For amount than being 20:80, conductive polymer material is polypyrrole；Solvent B is the mixed liquor of water and tetrahydrofuran, water and tetrahydrofuran
Volume ratio is 3:1；
The mass ratio of metal salt and the conductive polymer material in component B is 2.5:20 in component A.
Embodiment 5
The compound binding agent applied to lithium-sulfur cell of the present embodiment, is made of component A and component B；
Component A includes transition metal organic coordination compounds and solvent A；Transition metal organic coordination compounds are matched by organic
Body, soluble transition metal reaction are made；The mass ratio of organic ligand, soluble transition metal salt and solvent A is 0.5:0.25:
99.75, organic ligand is 1- vinyl imidazole, and soluble transition metal salt is zinc nitrate；Solvent A is water, dimethyl acetamide
With the mixed liquor of ethyl alcohol, the volume ratio of water, dimethyl acetamide and ethyl alcohol is 2:1:1；
Component B is made of conductive polymer material (i.e. binder) and solvent B, the matter of conductive polymer material and solvent B
For amount than being 1.5:98.5, conductive polymer material is poly- furans；Solvent B is the mixed liquor of water and tetrahydrofuran, water and tetrahydro furan
The volume ratio muttered is 3:1；
The mass ratio of metal salt and the conductive polymer material in component B is 0.25:1.5 in component A.
Embodiment 6
The compound binding agent applied to lithium-sulfur cell of the present embodiment, is made of component A and component B；
Component A includes transition metal organic coordination compounds and solvent A；Transition metal organic coordination compounds are matched by organic
Body, soluble transition metal reaction are made；The mass ratio of organic ligand, soluble transition metal salt and solvent A is 5:0.5:
94.5, organic ligand be 1- vinyl imidazole, soluble transition metal salt be nickel acetate, solvent A be water, dimethyl acetamide and
The mixed liquor of ethyl alcohol, the volume ratio of water, dimethyl acetamide and ethyl alcohol are 2:1:1；
Component B is made of conductive polymer material (i.e. binder) and solvent B, the matter of conductive polymer material and solvent B
For amount than being 5:95, conductive polymer material is polyselenophenes, and solvent B is the mixed liquor of water and dimethylformamide, water and dimethyl
The volume ratio of formamide is 4:1；
The mass ratio of metal salt and the conductive polymer material in component B is 0.5:5 in component A.
Embodiment 7
The lithium-sulphur cell positive electrode binder of the present embodiment, with the compound binding agent for being applied to lithium-sulfur cell in embodiment 1
Difference is only that: the conductive polymer material (i.e. binder) in component B is poly.
Embodiment 8
The compound binding agent applied to lithium-sulfur cell of the present embodiment, in embodiment 1 be applied to lithium-sulfur cell it is compound
The difference of binder is only that: the conductive polymer material in component B is replaced with into Kynoar (PVDF, i.e. binder),
Solvent B replaces with N-Methyl pyrrolidone.
The compound binding agent applied to lithium-sulfur cell in above-described embodiment is bi-component compound binding agent, component when use
A and component B realizes mixing；It is prepared by the preparation method that these bi-component compound binding agents can be used in following example 9.
Embodiment 9
The preparation method of the compound binding agent applied to lithium-sulfur cell of the present embodiment, comprising:
1) organic ligand, soluble transition metal salt and solvent A for taking formula ratio, by organic ligand and soluble transition gold
Belong to being milled in salt addition solvent A and be completely dispersed, component A is made；
2) binder and solvent B for taking formula ratio are completely dispersed being milled in binder addition solvent B, component are made
B。
Embodiment 10
The preparation method of the lithium-sulfur cell positive plate of the present embodiment, comprising the following steps: by sulfenyl composite material, acetylene
Black and binder is mixed according to the ratio that mass ratio is 8:1:1, is added in deionized water and is carried out ball milling, positive slurry is made
Then anode sizing agent is coated on aluminium foil, is subsequently placed in vacuum oven, in 60 DEG C of drying 12h after vacuumizing, is made by material
Carrying sulfur content is about 4mg/cm2Pole piece to get；Used sulfenyl composite material is mesoporous carbon/sulphur composite material, the quality of sulphur
Percentage composition is 69.5%；Used binder is the compound binding agent applied to lithium-sulfur cell in embodiment 1, and preparation is just
When the slurry of pole, the component A of compound binding agent for being applied to lithium-sulfur cell is uniformly mixed with component B, then with sulfenyl composite material,
Acetylene black is mixed.
Embodiment 11
The preparation method of the lithium-sulfur cell positive plate of the present embodiment, comprising the following steps: by sulfenyl composite material, superconduction
Carbon and binder are mixed according to the ratio that mass ratio is 8:1:1, are added in deionized water and are carried out ball milling, positive slurry is made
Then anode sizing agent is coated on aluminium foil, is subsequently placed in vacuum oven, in 60 DEG C of drying 12h after vacuumizing, is made by material
Carrying sulfur content is about 5mg/cm2Pole piece to get；Used sulfenyl composite material is mesoporous carbon/sulphur composite material, the quality of sulphur
Percentage composition is 69.5%；Used binder is the compound binding agent applied to lithium-sulfur cell in embodiment 2, and preparation is just
When the slurry of pole, the component A of compound binding agent for being applied to lithium-sulfur cell is uniformly mixed with component B, then with sulfenyl composite material,
Acetylene black is mixed.
Embodiment 12
The preparation method of the lithium-sulfur cell positive plate of the present embodiment, comprising the following steps: by sulfenyl composite material, superconduction
The ratio that carbon and binder are 8:1:1 according to mass ratio, is added in deionized water and carries out ball milling, anode sizing agent is made, and then will
Anode sizing agent is coated on aluminium foil, is subsequently placed in vacuum oven, in 60 DEG C of drying 12h after vacuumizing, is made and is carried sulfur content about
For 6mg/cm2Pole piece to get；Used sulfenyl composite material is mesoporous carbon/sulphur composite material, the mass percentage of sulphur
It is 69.5%；Used binder is the compound binding agent applied to lithium-sulfur cell in embodiment 3, prepares anode sizing agent
When, the component A of compound binding agent for being applied to lithium-sulfur cell is uniformly mixed with component B, then with sulfenyl composite material, acetylene black
It is mixed.
Embodiment 13~17
The preparation method of the lithium-sulfur cell of embodiment 13~17 positive plate is shown in Table 1, and the content that do not address is with embodiment 10:
The embodiment 13~17 of the preparation method of 1 lithium-sulfur cell positive plate of table
Comparative example
The preparation method of the lithium-sulfur cell positive plate of this comparative example, comprising the following steps:
1) M-phthalic acid and cobalt chloride are dissolved in water/tetrahydrofuran mixed liquor, are milled to and are completely dispersed, obtains mixing molten
Liquid, the mass fraction of M-phthalic acid and cobalt chloride is respectively 5% and 0.5% in mixed solution；
2) it then by gained mixed solution in 60 DEG C of reaction 5h, filters, is dry, obtaining hybrid inorganic-organic materials；
3) sulphur and hybrid inorganic-organic materials are obtained into sulfenyl composite material in 155 DEG C of processing 6h；Sulfenyl composite material
The mass percent of middle sulphur is 68%；
4) using sulfenyl composite material made from this comparative example according to the preparation of lithium-sulfur cell positive plate in embodiment 10
Lithium-sulfur cell positive plate is made in method.
Experimental example 1
This experimental example lithium-sulfur cell obtained using in embodiment 10 uses positive plate as positive plate, using lithium metal as cathode
Piece, with the LiNO of 0.1mol/L3Solution (solvent of use by 1,3- dioxolanes (DOL) and glycol dimethyl ether (DME) according to
The ratio of volume ratio 1:1 is mixed to get) it is used as electrolyte, it is assembled into Soft Roll lithium-sulfur cell (2Ah)；By the Soft Roll lithium sulphur electricity of assembling
Pond carries out electric performance test, the result is shown in Figure 1 under 25 DEG C, the charge-discharge magnification of 0.1C/0.1C.
As shown in Figure 1, charging/discharging voltage-capacity curve has typical lithium and sulfur chemistry response feature, the second electric discharge electricity
Flattening bench (2.05V) is steady and long, illustrates S6To S2The reaction of/S is more abundant, this is because of the invention is applied to lithium-sulfur cell
Composite caking agent there is sub (organic-inorganic pore structure) double grading of conductive (conductive polymer material)/diversion, make conduction
Even if the sulphur and sulphur compound of property difference are in the high (4mg/cm under carrying sulphur of pole piece2) more sufficient electrochemical reaction can also be carried out.
Experimental example 2
This experimental example is respectively with lithium-sulfur cell anode in the pole piece and comparative example that are prepared in embodiment 10~17
Piece is as positive plate, using lithium piece as negative electrode tab, with the LiNO of 0.1mol/L3(solvent of use is by 1,3- dioxolanes for solution
(DOL) it is mixed to get with glycol dimethyl ether (DME) according to the ratio of volume ratio 1:1) as electrolyte, it is assembled in glove box
At button cell；It is A1~A8 and B by the button cell number consecutively after assembling.
Each button cell is tested respectively under 25 DEG C, the charge-discharge magnification of 0.1C/0.1C, first discharge specific capacity and
The later specific capacity of 100 circulations, test result are shown in Table 2, and wherein the cycle-index of button cell A1-specific capacity performance map is shown in
The cycle-index of Fig. 2, button cell A2-specific capacity performance map are shown in Fig. 3, cycle-index-specific capacity performance of button cell A3
Figure is shown in Fig. 4.Specific discharge capacity is the ratio of capacitance and active material quality.
2 first discharge specific capacity of table and circulation 100 times after specific discharge capacity
As shown in Table 1, it can be improved the head of lithium-sulfur cell using the compound binding agent applied to lithium-sulfur cell of the invention
Secondary specific discharge capacity and specific discharge capacity.
Claims (7)
1. a kind of compound binding agent applied to lithium-sulfur cell, it is characterised in that: including transition metal organic coordination compounds and
Binder；The transition metal organic coordination compounds are made by organic ligand and soluble transition metal reactant salt；It is described viscous
The mass ratio for tying agent, organic ligand and soluble transition metal salt is 1.5~20:0.5~10:0.25~2.5.
2. the compound binding agent according to claim 1 applied to lithium-sulfur cell, it is characterised in that: the binder is to lead
Electric high molecular material.
3. the compound binding agent according to claim 2 applied to lithium-sulfur cell, it is characterised in that: the conducting polymer
Material is selected from least one of polyaniline, polypyrrole, polythiophene, poly- furans, polyselenophenes, poly, polyphenylene sulfide.
4. the compound binding agent according to any one of claims 1 to 3 applied to lithium-sulfur cell, it is characterised in that:
The compound binding agent applied to lithium-sulfur cell includes component A and component B；The component A includes that the transition metal is organic
Complex and solvent A；The component B includes the conductive polymer material and solvent B.
5. a kind of preparation method of the compound binding agent applied to lithium-sulfur cell, it is characterised in that: include:
Organic ligand and soluble transition metal salt are uniformly mixed in solvent A, obtain component A；
Binder and solvent B are uniformly mixed, component B is obtained；
The mass ratio of the binder, organic ligand and soluble transition metal salt is 1.5~20:0.5~10:0.25~2.5.
6. the preparation method of the compound binding agent according to claim 5 applied to lithium-sulfur cell, it is characterised in that: described
Binder is conductive polymer material.
7. the preparation method of the compound binding agent according to claim 6 applied to lithium-sulfur cell, it is characterised in that: described
Conductive polymer material in polyaniline, polypyrrole, polythiophene, poly- furans, polyselenophenes, poly, polyphenylene sulfide extremely
Few one kind.
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