CN109659513A - A kind of sulphur positive electrode, anode and lithium-sulfur cell containing the material - Google Patents

A kind of sulphur positive electrode, anode and lithium-sulfur cell containing the material Download PDF

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Publication number
CN109659513A
CN109659513A CN201811382513.8A CN201811382513A CN109659513A CN 109659513 A CN109659513 A CN 109659513A CN 201811382513 A CN201811382513 A CN 201811382513A CN 109659513 A CN109659513 A CN 109659513A
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positive electrode
lithium
carbon
sulphur
sulfur
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李中
吴军
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Zhongxing High Energy Technology Co Ltd
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Zhongxing High Energy Technology 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
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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
    • 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

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  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The present invention relates to a kind of sulphur positive electrodes, anode and lithium-sulfur cell containing the material.The sulphur positive electrode, with the total weight of the sulphur positive electrode, the sulphur positive electrode includes: the sulfur-bearing active material of 60wt%~80wt%；The first conductive carbon of 5wt%~20wt%；The cation type polymer electrolyte of 20wt%~40wt%；With the first binder of 3wt%~10wt%.Sulphur anode including the sulphur positive electrode can effectively be anchored the polysulfide generated when sulfur electrode charging and discharging, can inhibit the shuttle of sulfide, obtain discharge capacity height, the excellent lithium-sulfur cell of cycle performance.

Description

A kind of sulphur positive electrode, anode and lithium-sulfur cell containing the material
Technical field
The invention belongs to lithium-sulfur cell fields, are more particularly to the sulphur anode of lithium-sulfur cell.
Background technique
Lithium-sulfur cell is a kind of secondary cell using sulphur as anode, lithium metal as cathode, theoretical energy density height It is 5~10 times of traditional commerce " rocking chair type " lithium ion battery energy density up to 2500Wh/kg.And elemental sulfur also has money Abundant, the at low cost and environmental-friendly advantage in source.So not being able to satisfy people to electric vehicle in current commercial Li-ion battery In the case that course continuation mileage requires, lithium-sulfur cell starts to obtain scientific research and business circles as one of alternative energy storage system Extensive concern and further investigation.
However, lithium-sulfur cell, there are also defect, these defects limit its commercial applications, one of them is lithium sulphur Battery more sulfides generate in charge and discharge process " shuttle effect ", so that battery capacity constantly declines, causes cyclicity The sharply deterioration of energy.In ethers electrolyte, elemental sulfur will form the soluble long-chain polysulphides of liquid in charge and discharge (Li2Sx, 4≤x≤8), soluble polysulfide can pass through under electric field force and concentration gradient effect between positive electrode and negative electrode Diaphragm moves to and fro, this phenomenon is just called " shuttle effect "." shuttle effect " can be such that active material sulphur is constantly lost, and make Constantly decline at the capacity of battery.
Only solve the problems, such as polysulfide " shuttle effect ", the cycle performance of lithium-sulfur cell can be just improved, and be This, researchers propose many strategies and make some progress, one of direction be for sulphur positive electrode into Row improves, for example, using carbon material (such as the hollow carbon balls, carbon nanometer of various patterns, dimension and structure in positive electrode Pipe, graphene, 3D porous carbon fiber etc.), metallic compound (such as TiO2、MnO2、Al2O3、CoS2、WS2、SnS2、TiN、VN Deng), conducting polymer (such as polyaniline (PANI), polypyrrole (PPy), polythiophene (PTh) etc.) etc., pass through physical barriers, inhale Attached or chemical anchoring the movement acted on to inhibit polysulfide.
But so far, efficiently inhibit the material of polysulfide " shuttle effect " in lithium-sulfur cell unsatisfactory.Mesh Before, it still needs to propose the problem of further suppressing " shuttle effect " solution, i.e., " confinement " is carried out to polysulfide, to obtain The lithium-sulfur cell of function admirable.
Summary of the invention
In view of this, the main purpose of the present invention is to provide a kind of improved positive electrode for lithium-sulfur cell and Anode can effectively prevent " shuttle effect " of the polysulfide between positive and negative anodes, to improve the cycle characteristics of lithium-sulfur cell.
On reaching above-mentioned, the first aspect of the present invention provides a kind of sulphur positive electrode, with the sulphur positive electrode Total weight, the sulphur positive electrode includes:
The sulfur-bearing active material of 60wt%~80wt%；
The first conductive carbon of 5wt%~20wt%；
The cation type polymer electrolyte of 5wt%~40wt%；With
The first binder of 3wt%~10wt%.
According to a kind of embodiment, cation type polymer electrolyte is polyelectrolyte containing ammonium cation.
According to a kind of embodiment, cation type polymer electrolyte is selected from polydimethyl diallyl ammonium chloride (PDMDAAC), poly- diethyl diallyl ammonium chloride (PDEDAAC), diethyl diallyl ammonium chloride-acrylamide copolymer At least one of (P (DE-AM)).
According to a kind of embodiment, it is multiple to be selected from elemental sulfur, carbon/sulphur composite material, metallic compound-sulphur for sulfur-bearing active material Condensation material, conducting polymer/at least one of sulphur composite material and metal sulfide.
According to a kind of embodiment, the first conductive carbon is selected from acetylene black, conductive carbon black, superconducting carbon black, Peal blackberry and Ke Qin It is at least one of black, preferably acetylene black and superconducting carbon black.
According to a kind of embodiment, first binder is selected from polytetrafluoroethylene (PTFE), Kynoar, beta-cyclodextrin, polyoxygenated At least one in ethylene, sodium alginate, polyvinylpyrrolidone, sodium carboxymethylcellulose, Arabic gum, gelatin and poly-dopamine Kind, preferably Kynoar.
According to the second aspect of the invention, a kind of anode for battery is additionally provided, comprising:
Collector；With
The positive electrode material layer on the collector is overlayed on, positive material described in the positive electrode material layer the first aspect of the present invention Material is constituted.
According to a kind of embodiment, anode further comprises the barrier layer overlayed on the positive electrode material layer, with barrier layer Total weight, barrier layer includes:
The second conductive carbon of 20wt%~30wt%；
The anionic polymer electrolyte of 40wt%~70wt%；
The second binder of 10wt%~40wt%.
According to a kind of embodiment, anionic polymer electrolyte is selected from double sulfimide class single-ion polymer lithiums At least one of salt, polyureas single-ion polymer lithium salts and perfluorosulfonic acid type polymer single ion lithium salts.
According to a kind of embodiment, the second conductive carbon is selected from active carbon, conductive carbon BP2000, conductive carbon XC-72, section's qin At least one of black, microporous carbon, carbon nano-fiber, carbon nanotube, mesoporous carbon, graphene and three-dimensional carbon materials, preferably Conductive carbon BP2000 and graphene.
According to a kind of embodiment, the second binder is selected from Kynoar, polyethylene glycol oxide, sodium alginate, polyethylene In pyrrolidones, sodium carboxymethylcellulose, Arabic gum, gelatin, poly-dopamine and Kynoar-hexafluoropropylene copolymer At least one, preferably Kynoar and polyethylene glycol oxide.
According to a kind of embodiment, the amount ratio of the second conductive carbon and anionic polymer electrolyte is 1:1~5, excellent It is selected as 1:1~3.
According to a kind of embodiment, barrier layer with a thickness of 5~30 μm, preferably 10~20 μm.
According to a kind of embodiment, positive 0.2~10mg/cm of sulphur carrying capacity2, preferably 0.5~5mg/cm2。
According to the third aspect of the invention we, a kind of lithium-sulfur cell is additionally provided, comprising: anode of the invention；Cathode；It is located at Diaphragm between anode and cathode；And electrolyte.
According to a kind of embodiment, wherein cathode is lithium electrode.
According to a kind of embodiment, lithium-sulfur cell is 70% or more in the discharge capacity retention rate of 100 charge and discharge cycles.
According to a kind of embodiment, the first discharge specific capacity of lithium-sulfur cell is 1200mAh/g or more.
By using the sulphur anode of multilayered structure prepared by the present invention, production when can effectively be anchored sulfur electrode charging and discharging Raw polysulfide can inhibit the shuttle of sulfide, obtain discharge capacity height, the excellent lithium-sulfur cell of cycle performance.
Detailed description of the invention
Fig. 1 is sulfur electrode structural schematic diagram of the invention；
First charge-discharge curve graph of the Fig. 2 for comparative example and the lithium-sulfur cell of sulfur electrode assembly of the invention at 0.2C；
Fig. 3 is cycle performance figure of the lithium-sulfur cell of comparative example assembled with sulfur electrode of the invention at 0.2C.
Specific embodiment
In order to elaborate Spirit Essence of the invention, given below in conjunction with the specific embodiment of attached drawing through the invention With explanation.It should be understood that following specific embodiments are merely to illustrate the present invention, and and it is not meant to limit the scope of the invention.
The present invention provides a kind of sulfur electrode of multilayered structure, structure is as shown in Figure 1.The sulfur electrode packet of the multilayered structure Include following three layers: collector 100, sulphur positive electrode material layer 101 and barrier layer 102.
The material of collector 100 can be those of to use in the prior art, such as can be aluminium, is also possible to and carbon, copper Or the excellence conductors such as silver.Specifically, collector can be one of aluminium foil, aluminium net, carbon net, carbon film, collector 100 of the invention An example be aluminium foil.
Sulphur positive electrode material layer 101 is coated on collector 100 by anode sizing agent and is formed, firstly, preparing anode sizing agent, this is just Pole slurry is mixed with the first dispersing agent by certain weight ratio by sulphur positive electrode.According to a kind of embodiment, sulphur Positive electrode, with the total weight of the sulphur positive electrode, comprising:
The sulfur-bearing active material of 60wt%~80wt%；
The first conductive carbon of 5wt%~20wt%；
The cation type polymer electrolyte of 5wt%~40wt%；With
The first binder of 3wt%~10wt%.
According to a kind of embodiment, the first conductive carbon cation type polymer electrolyte and sulfur-bearing active material cationic The amount ratio of polymer dielectric is 1:2~10, preferably 1:2~8.Wherein, sulfur-bearing active positive electrode material can be selected from simple substance In sulphur, carbon/sulphur composite material, metallic compound/sulphur composite material, conducting polymer/sulphur composite material and metal sulfide It is at least one.According to a preferred embodiment, sulfur-bearing active positive electrode material is carbon/sulphur composite material, in particular acetylene Black/sulphur composite material.According to another preferred embodiment, sulfur-bearing active positive electrode material is metallic compound/sulphur composite wood Material, in particular Al2O3/ sulfur compound.
Wherein, conductive carbon is selected from least one of acetylene black, conductive carbon black, superconducting carbon black, Peal blackberry, Ketjen black etc.. According to a preferred embodiment, conductive carbon is acetylene black and superconducting carbon black.
Wherein, the polymer salt with fixed cation is selected from polydimethyl diallyl ammonium chloride (PDMDAAC), poly- two In ethyl diallyl ammonium chloride (PDEDAAC) and diethyl diallyl ammonium chloride-acrylamide copolymer (P (DE-AM)) At least one.According to a preferred embodiment, the polymer salt with fixed cation is poly dimethyl allyl Ammonium chloride (PDMDAAC).
Wherein, first binder is selected from polytetrafluoroethylene (PTFE), Kynoar, beta-cyclodextrin, polyethylene glycol oxide, alginic acid At least one of sodium, polyvinylpyrrolidone, sodium carboxymethylcellulose, Arabic gum, gelatin and poly-dopamine.According to one Preferred embodiment, binder are Kynoar.
Wherein, the first dispersing agent be selected from N-Methyl pyrrolidone, n,N-Dimethylformamide, n,N-dimethylacetamide, At least one of tetrahydrofuran, dimethyl sulfoxide, isopropanol, ethyl alcohol and ether.According to a preferred embodiment, dispersing agent For N-Methyl pyrrolidone.
After preparation is with above-mentioned anode sizing agent, which is coated on collector 100 with method well known in the art Surface, after dry out solvent, thus form sulphur positive electrode material layer 101.
In sulphur positive electrode material layer 101, since more sulfides in polysulfide are negatively charged, so with fixed sun The polymer salt of ion can be anchored polysulfide by electrostatic attraction effect, limit the movement of polysulfide.
Similar, barrier layer 102 is coated on sulphur positive electrode material layer 101 by barrier slurry and is formed.It is specific according to one Embodiment, barrier slurry are mixed with by the material and the second dispersing agent for constituting barrier layer by certain weight ratio.
According to a specific embodiment, the barrier layer on the positive electrode material layer is overlayed on, with the total of the barrier layer Poidometer, the barrier layer include:
The second conductive carbon of 20wt%~30wt%；
The anionic polymer electrolyte of 40wt%~70wt%；
The second binder of 10wt%~40wt%.
The optimal ratio of dispersing agent can be then determined by experiment.
According to a kind of embodiment, the amount ratio of the second conductive carbon and anionic polymer electrolyte is 1:1~5, excellent It is selected as 1:1~3.
Wherein, the second conductive carbon is selected from active carbon, conductive carbon BP2000, conductive carbon XC-72, Ketjen black, microporous carbon, carbon and receives At least one of rice fiber, carbon nanotube, mesoporous carbon, graphene and three-dimensional carbon materials.According to a preferred embodiment party Formula, the second conductive carbon are conductive carbon BP2000 and graphene.
Second conductive carbon and the first conductive carbon can be the same or different.
Wherein, anionic polymer electrolyte is selected from double sulfimide class single-ion polymer lithium salts, polyureas single ion At least one of polymer lithium salts and perfluorosulfonic acid type single-ion polymer lithium salts.According to a preferred embodiment, yin Ionomer electrolyte is perfluorosulfonic acid type polymer single ion lithium salts (Li-Nafion).
Wherein, the second binder is selected from Kynoar, polyethylene glycol oxide, sodium alginate, polyvinylpyrrolidone, carboxylic first At least one of base sodium cellulosate, Arabic gum, gelatin, poly-dopamine and Kynoar-hexafluoropropylene copolymer.According to One preferred embodiment, the second binder are Kynoar.
Second conductive carbon and the first conductive carbon can be the same or different.
Wherein, the second dispersing agent be selected from n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, At least one of isopropanol, ethyl alcohol, ether, tetrahydrofuran and dimethyl sulfoxide.According to a preferred embodiment, second point Powder is N-Methyl pyrrolidone.
Similarly, after by Multifunctional sizing agent described in above method, which is coated on sulphur anode material The surface of the bed of material 101 after dry out solvent, thus forms barrier layer 102, i.e. multi-functional coatings.
Since anionic polymer electrolysis mass-energy stops polysulfide by electrostatic repulsion forces, and due to porous carbon With very strong physical absorption ability, very strong suction-operated can be also generated to polysulfide, therefore barrier layer 102 can be further Inhibit the diffusion of polysulfide.
According to a specific embodiment, the sulphur anode material formed by above-mentioned sulphur positive electrode material layer 101 and barrier layer 102 Sulphur carrying capacity in material is 0.2~10mg/cm2.According to a preferred embodiment, the sulphur carrying capacity in sulphur positive electrode is 0.5 ~5mg/cm2。
According to a specific embodiment, barrier layer with a thickness of 5 microns~30 microns, preferably 10 microns~20 is micro- Rice can determine most suitable thickness according to test.
In order to preferably illustrate particular content and effect of the invention, following embodiment is simultaneously described in detail in conjunction with attached drawing Beneficial effects of the present invention.
Embodiment 1:
Prepare anode sizing agent
Anode sizing agent is by acetylene black/sulfur compound (positive electrode active materials), conductive carbon black (conductive carbon), Kynoar (binder), the PDMDAAC polymer salt of cation (fixed), N-Methyl pyrrolidone (dispersing agent) composition, wherein acetylene black/ Sulfur compound, conductive carbon black, Kynoar, PDMDAAC mass ratio be 70:5:5:20.It stirs evenly, reaches to anode sizing agent To after suitable solid content and viscosity, this slurry is coated in current collector aluminum foil, 60 DEG C of forced air drying 2h, 60 DEG C of vacuum drying The sulphur active material layer on aluminium foil is obtained after 12h.
Prepare multi-functional coatings slurry
The slurry of multi-functional coatings is (conductive more by Li-Nafion (anionic polymer electrolyte), conductive carbon BP2000 Hole carbon), Kynoar (binder), N-Methyl pyrrolidone (dispersing agent) composition, wherein Li-Nafion, conductive carbon BP2000, Kynoar mass ratio be 5:3:2.It is uniform to this slurry agitation, it, will after reaching suitable solid content and viscosity This slurry is coated in the above-mentioned sulphur active material layer surface with aluminium foil, 60 DEG C of forced air drying 2h, 60 DEG C of vacuum drying 12h Afterwards, be cut into the disk that diameter is 16mm obtain first layer be aluminium foil, the second layer be the sulphur active material containing functional additive Layer and third layer are the sulfur electrode of multi-functional coatings, and the carrying capacity of active material sulphur is 2.5mg/cm on sulfur electrode2。
Comparative example 1:
In order to prove the validity of sulfur electrode structure proposed by the present invention, comparative experiments is devised.Sulphur in comparative experiments Electrode is the common sulfur electrode under the prior art, and preparation method is as follows.
The anode sizing agent of common sulfur electrode is by acetylene black/sulfur compound (positive electrode active materials), conductive carbon black (Super P) (conductive carbon), Kynoar (binder), N-Methyl pyrrolidone (dispersing agent) composition, wherein acetylene black/sulfur compound, lead Electrical carbon is black, Kynoar mass ratio is 9:5:5.It is stirred evenly to anode sizing agent, after reaching suitable solid content and viscosity, This slurry is coated in current collector aluminum foil, the original that diameter is 16mm is cut into 60 DEG C of forced air drying 4h, 60 DEG C of vacuum drying afterwards for 24 hours Piece be obtain first layer be aluminium foil, the second layer be the sulphur active material layer without containing functional additive common sulfur electrode, commonly The carrying capacity of active material sulphur also controls as 2.5mg/cm on sulfur electrode2。
Test:
In the glove box of argon atmosphere, using the two kinds of sulfur electrodes prepared in above-described embodiment 1 and comparative example 1 as just Pole, PP film use ethers business electrolyte (1M LiTFSI/DOL&DME, 1wt% as cathode as diaphragm, metal lithium sheet LiNO3) it is assembled into the button cell of CR2025.
Conclusion:
The charge-discharge test of battery carries out on blue electric tester.Investigate two kinds of sulfur electrode electricity of embodiment 1 and comparative example 1 The discharge capacity and cycle performance in pond.As shown in Fig. 2, it as a result see the table below 1.
Table 1:
Embodiment 2:
Anode sizing agent is by Al2O3/ sulfur compound (positive electrode active materials), acetylene black (conductive carbon), Kynoar (bonding Agent), the PDEDAAC polymer salt of cation (fixed), N-Methyl pyrrolidone (dispersing agent) composition, wherein Al2O3/ sulphur is compound Object, acetylene black, Kynoar, PDEDAAC mass ratio be 60:5:5:30.It is stirred evenly to anode sizing agent, reaches suitable After solid content and viscosity, this slurry is coated in current collector aluminum foil, after 60 DEG C of forced air drying 2h, 60 DEG C of vacuum drying 12h i.e. Obtain the sulphur active material layer on aluminium foil.
The slurry for preparing multi-functional coatings (is led by Li-Nafion (anionic polymer electrolyte), conductive carbon BP2000 Electric porous carbon), Kynoar (binder), N-Methyl pyrrolidone (dispersing agent) composition, wherein Li-Nafion, conductive carbon BP2000, Kynoar mass ratio be 5:3:2.It is uniform to this slurry agitation, it, will after reaching suitable solid content and viscosity This slurry is coated in the above-mentioned sulphur active material layer surface with aluminium foil, 60 DEG C of forced air drying 2h, 60 DEG C of vacuum drying 12h Afterwards, be cut into the disk that diameter is 16mm obtain first layer be aluminium foil, the second layer be the sulphur active material containing functional additive Layer and third layer are the sulfur electrode of multi-functional coatings, and the carrying capacity of active material sulphur is 2.5mg/cm on sulfur electrode2。
Test:
In the glove box of argon atmosphere, using the above-mentioned sulfur electrode prepared as anode, PP film is as diaphragm, lithium metal Piece uses ethers business electrolyte (1M LiTFSI/DOL&DME, 1wt%LiNO as cathode3) it is assembled into the button of CR2025 Battery.
The charge-discharge test of battery carries out on blue electric tester.Investigate the charge/discharge capacity and cycle performance of battery.Electricity For the first time discharge capacity of the pond at 0.2C can reach 1367.8mAh/g；And it remains to release 982.4mAh/g after 100 circulations Capacity, discharge capacitance reached 71.8%.
The foregoing is merely the preferred embodiment of the present invention, are not intended to limit the scope of the invention, it is all Under inventive concept of the invention, made equivalent transformation or modification, or directly/to be used in other related technical areas equal indirectly It is included within the scope of the present invention.

Claims (19)

1. a kind of sulphur positive electrode, with the total weight of the sulphur positive electrode, the sulphur positive electrode includes:
The sulfur-bearing active material of 60wt%~80wt%；
The first conductive carbon of 5wt%~20wt%；
The cation type polymer electrolyte of 5wt%~40wt%；With
The first binder of 3wt%~10wt%.
2. positive electrode according to claim 1, the cation type polymer electrolyte is containing the poly- electrolysis of ammonium cation Matter.
3. positive electrode according to claim 2, the polyelectrolyte containing ammonium cation is selected from poly dimethyl allyl Ammonium chloride (PDMDAAC), poly- diethyl diallyl ammonium chloride (PDEDAAC), diethyl diallyl ammonium chloride-acrylamide At least one of copolymer (P (DE-AM)).
4. positive electrode according to claim 1, the sulfur-bearing active material is selected from elemental sulfur, carbon/sulphur composite material, gold Belong to compound-sulphur composite material, conducting polymer/at least one of sulphur composite material and metal sulfide.
5. positive electrode according to claim 1, first conductive carbon be selected from acetylene black, conductive carbon black, superconducting carbon black, At least one of Peal blackberry and Ketjen black, preferably acetylene black and superconducting carbon black.
6. positive electrode according to claim 1, the first binder is selected from polytetrafluoroethylene (PTFE), Kynoar, β- Cyclodextrin, polyethylene glycol oxide, sodium alginate, polyvinylpyrrolidone, sodium carboxymethylcellulose, Arabic gum, gelatin and poly- more At least one of bar amine, preferably Kynoar.
7. positive electrode according to claim 1, the cation type polymer electrolyte and the sulfur-bearing active material Amount ratio be 1:2~10, preferably 1:2~8.
8. a kind of anode for battery, comprising:
Collector；With
The positive electrode material layer on the collector is overlayed on, the positive electrode material layer is by such as according to any one of claims 1 to 7 Positive electrode is constituted.
9. anode according to claim 8, further comprises, the barrier layer on the positive electrode material layer is overlayed on, with described The total weight on barrier layer, the barrier layer include:
The second conductive carbon of 20wt%~30wt%；
The anionic polymer electrolyte of 40wt%~70wt%；
The second binder of 10wt%~40wt%.
10. anode according to claim 9, the anionic polymer electrolyte is selected from double sulfimide class single ions At least one of polymer lithium salts, polyureas single-ion polymer lithium salts and perfluorosulfonic acid type polymer single ion lithium salts.
11. anode according to claim 9, second conductive carbon is selected from active carbon, conductive carbon BP2000, conductive carbon At least one in XC-72, Ketjen black, microporous carbon, carbon nano-fiber, carbon nanotube, mesoporous carbon, graphene and three-dimensional carbon materials Kind, preferably conductive carbon BP2000 and graphene.
12. anode according to claim 9, the second binder be selected from Kynoar, polyethylene glycol oxide, sodium alginate, Polyvinylpyrrolidone, sodium carboxymethylcellulose, Arabic gum, gelatin, poly-dopamine and Kynoar-hexafluoropropene copolymerization At least one of object, preferably Kynoar and polyethylene glycol oxide.
13. the amount ratio of anode according to claim 9, the second conductive carbon and anionic polymer electrolyte is 1:1 ~5, preferably 1:1~3.
14. anode according to claim 9, the barrier layer with a thickness of 5~30 μm, preferably 10~20 μm.
15. anode according to claim 9,0.2~10mg/cm of sulphur carrying capacity of the anode2, preferably 0.5~5mg/ cm2。
16. a kind of lithium-sulfur cell, comprising: the anode according to any one of claim 8~15；Cathode；Positioned at it is described just Diaphragm between pole and the cathode；And electrolyte.
17. lithium-sulfur cell according to claim 16, the cathode is lithium electrode.
18. lithium-sulfur cell according to claim 16, the lithium-sulfur cell is protected in the discharge capacity of 100 charge and discharge cycles Staying rate is 70% or more.
19. lithium-sulfur cell according to claim 16, the first discharge specific capacity of the lithium-sulfur cell be 1200mAh/g with On.
CN201811382513.8A 2018-11-20 2018-11-20 A kind of sulphur positive electrode, anode and lithium-sulfur cell containing the material Pending CN109659513A (en)

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Application publication date: 20190419