CN103682361A - Adhesive for anode of lithium sulfur battery and application of adhesive to preparation of lithium sulfur battery - Google Patents
Adhesive for anode of lithium sulfur battery and application of adhesive to preparation of lithium sulfur battery Download PDFInfo
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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
- H01M4/622—Binders being polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
- C08L1/26—Cellulose ethers
- C08L1/28—Alkyl ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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
Abstract
The invention belongs to the field of battery adhesives and provides an adhesive for an anode of a lithium sulfur battery. The adhesive consists of 50 to 95 wt% of gelatinized starch and 5 to 50 wt% of an additive, wherein the additive is at least one of carboxymethyl cellulose sodium and polyvinyl alcohol. The invention also provides application of the adhesive to preparation of the lithium sulfur battery. When the adhesive is applied to preparation of the lithium sulfur battery, the cycling performance of the lithium sulfur battery can be greatly improved.
Description
Technical field
The invention belongs to battery binding agent field, particularly binding agent and the application in lithium-sulfur cell preparation thereof for a kind of lithium-sulphur cell positive electrode.
Background technology
Flourish along with consumer electronics market, the power consumption of the mobile electronic device such as the consumption such as mobile phone, notebook computer constantly increases, and the preference of consumer to light and thin type electronic product, and these are all had higher requirement to the energy density of lithium battery.And traditional lithium ion battery aspect energy density difficulty be greatly improved, in this case, the lithium-sulfur cell with high theoretical energy density has caused people's extensive concern.It is positive active material that lithium-sulfur cell be take elemental sulfur or other sulfur-bearing active materials conventionally, and ether solvent or the ionic liquid that is dissolved with lithium salts of take is electrolyte, and take lithium metal or other is negative pole containing lithium material.Although lithium-sulfur cell has advantage aspect energy density, its theoretical energy density reaches as high as 2600Wh/kg, and its loop attenuation is too fast, is difficult to meet the demand of commercial applications.
Because general lithium-sulphur cell positive electrode is still continued to use the anodal binding agent Kynoar of business lithium electricity, this binding agent Swelling in lithium-sulfur cell ethers electrolyte used is serious, adhesive property easily declines, and causes lithium-sulphur cell positive electrode capacity attenuation in cyclic process larger.Meanwhile, the price of Kynoar is relatively high, uses it as anodal binding agent, can cause the production cost of lithium-sulfur cell too high.Kynoar generally will could be dissolved with the more expensive organic solvent of the prices such as 1-METHYLPYRROLIDONE in use, 1-METHYLPYRROLIDONE boiling point is higher, cause electrode slice baking temperature high, drying time is long, and this easily makes the elemental sulfur volatilization in electrode slice and produces capacitance loss.In addition, 1-METHYLPYRROLIDONE also has certain toxicity, and its rat median lethal dose is 3.8mL/kg, and long-term suction can cause central nervous system dysfunction.
Have researcher to adopt CMC and butadiene-styrene rubber mixture or animal gelatin as anodal binding agent, improved to a certain extent the cycle performance of lithium-sulfur cell, but its cycle-index less than 100 times is still difficult to compete mutually with commercial Li-ion batteries.In addition, because butadiene-styrene rubber contains comparatively active carbon-carbon double bond, intermediate product easy and lithium-sulfur cell electrode reaction reacts, animal gelatin is comparatively responsive to acid, alkali, enzyme, heat etc., less stable, facile hydrolysis is low-molecular-weight polypeptide, and therefore, the more good lithium-sulfur cell of exploitation performance is very important with anodal binding agent.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of lithium-sulphur cell positive electrode binding agent is provided, the good stability of described binding agent in ethers electrolyte, can significantly promote its cyclical stability while being applied to lithium-sulphur cell positive electrode, has higher actual application value.
Lithium-sulphur cell positive electrode provided by the invention comprises gelatinized starch with binding agent.
In technique scheme, described binding agent is comprised of the gelatinized starch of 50～95wt% and the additive of 50～5wt%.
In technique scheme, described additive is at least one in sodium cellulose glycolate, polyvinyl alcohol; Add the storage performance that polyvinyl alcohol can improve binding agent of the present invention; In use, the viscosity of the adjustable binding agent slurry of sodium cellulose glycolate, the uniformity of coating when strengthening the compatibility between each component and filming.
In technique scheme, described binding agent is preferably by the gelatinized starch of 70～95wt% and the additive of 30～5wt% and forms, and more preferably the gelatinized starch of 85～95wt% and the additive of 15～5wt%, consists of.
In technique scheme, when additive is sodium cellulose glycolate and polyvinyl alcohol, the mass ratio of sodium cellulose glycolate and polyvinyl alcohol is 1:4～4:1.
In technique scheme, gelatinized starch plays cementation, starch is carried out in hot water after gelatinization processing, obtain gelatinized starch, when processing, gelatinization can add the alkaline matters such as the oxidants such as hydrogen peroxide, hypochlorite or lithium hydroxide to reduce gelatinization point, promote the carrying out of gelatinization process, improve the performance of gelatinization product.Specifically can be prepared as follows gelatinized starch: to the hydrogenperoxide steam generator that adds 3 mass parts water and 0.3 mass parts 30wt% in 1 mass parts soluble starch, after mixing, at 58 ℃, be incubated 2 hours, then add 0.3 mass parts lithium hydroxide and mix, 58 ℃ of insulations 2 hours, finally by products therefrom 100 ℃ of insulations to removing moisture, obtain.
Lithium-sulphur cell positive electrode of the present invention is as follows by the preparation method of binding agent: according to ratio metering gelatinized starch and the additive in above-mentioned binder formula, then their are ground or are milled to and mix and get final product.
The present invention also provides the application of a kind of above-mentioned binding agent in lithium-sulfur cell preparation.
Adopt described lithium-sulphur cell positive electrode to be generally by the process that binding agent is prepared lithium-sulphur cell positive electrode: described lithium-sulphur cell positive electrode is mixed in proportion with binding agent and sulfur-bearing active material, conductive agent, then be dispersed in and in water, make slurry, or first described lithium-sulphur cell positive electrode is scattered in water with binding agent, then add sulfur-bearing active material with conductive agent and mix to make slurry; Gained slurry is evenly coated in conductive current collector, dry, obtain lithium-sulphur cell positive electrode;
Described sulfur-bearing active material is elemental sulfur, many lithium sulfides Li
2s
n(1≤n≤8), sulfenyl composite material, organic sulfur compound or sulphur carbon polymer, wherein, described sulfenyl composite material comprises the composite material that elemental sulfur and material with carbon element or conducting polymer are made etc., and described organic sulfur compound comprises the sulfuration macromolecular material that sulphur at high temperature forms with polyacrylonitrile, polyethylene etc.; Described conductive agent is carbon black, carbon nano-tube, Graphene, graphite powder, graphite flake, metal oxide or conducting polymer composite etc.; Described collector is foam metal, foamy carbon, metal forming, cover the electric conducting materials such as carbon metal forming, wire netting, carbon cloth, carbon felt or graphene film.
In above-mentioned application, the amount of described water is 3～10 times that described lithium-sulphur cell positive electrode is used binding agent quality, and described water is distilled water or deionized water.
In above-mentioned application, when sulfur-bearing active material is elemental sulfur, conductive agent while being carbon black, the amount of elemental sulfur be described lithium-sulphur cell positive electrode with 7 times of binding agent quality, the amount of carbon black is that described lithium-sulphur cell positive electrode is with 2 times of binding agent quality.
Compared with prior art, the present invention has following beneficial effect:
1, the invention provides a kind of new lithium-sulphur cell positive electrode binding agent, when preparing lithium-sulfur cell, use this binding agent can significantly promote the cycle performance (seeing embodiment 12) of lithium-sulfur cell, experiment shows, uses the capability retention that the lithium-sulfur cell of binding agent of the present invention circulates after 100 times under 0.2C current density to reach as high as 96%.
2, the cheap and safety non-toxic of each component of binding agent provided by the invention, take water as dissolution with solvents during use, and environmental protection, has cost and environmental advantage concurrently.
3, to take in use the relatively low water of boiling point be dissolution with solvents to binding agent of the present invention, thereby when battery pole piece is dry, without adding solvent recovery unit, operate more simple, and electrode slice is drier, thereby can shorten the Production Time of electrode slice.
Accompanying drawing explanation
Fig. 1 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 1 and comparative example.
Fig. 2 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 2 and comparative example.
Fig. 3 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 3 and comparative example.
Fig. 4 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 4 and comparative example.
Fig. 5 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 5 and comparative example.
Fig. 6 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 6 and comparative example.
Fig. 7 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 7 and comparative example.
Fig. 8 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 8 and comparative example.
Fig. 9 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 9 and comparative example.
Figure 10 is the cycle performance figure of the lithium-sulfur cell of example preparation in embodiment 10 and contrast.
Figure 11 is the cycle performance figure of the lithium-sulfur cell prepared in embodiment 11 and comparative example.
Embodiment
Below by embodiment, also by reference to the accompanying drawings lithium-sulphur cell positive electrode of the present invention is described further with binding agent and preparation method thereof and application.
In following each embodiment, the hydrogenperoxide steam generator of described 30wt% is purchased from Chengdu Ke Long chemical reagent factory; It is pure that described LiOH, polyvinyl alcohol, sodium cellulose glycolate, soluble starch and elemental sulfur powder are analysis, purchased from Chengdu Ke Long chemical reagent factory; Described barrier film is purchased from Celgard company, and model is 2325; Described carbon black is purchased from Switzerland Te Migao company, and commodity are called Super P Li.
In following each embodiment, the preparation method of described gelatinized starch is: to the hydrogenperoxide steam generator that adds 3 mass parts deionized waters and 0.3 mass parts 30wt% in 1 mass parts soluble starch, after mixing, at 58 ℃, be incubated 2 hours, then add 0.3 mass parts LiOH and mix, 58 ℃ of insulations 2 hours, finally products therefrom is incubated to 20 hours at 100 ℃, obtains gelatinized starch.
Embodiment 1
The present embodiment be take gelatinized starch as lithium-sulphur cell positive electrode binding agent, 1 mass parts gelatinized starch is joined in 3 mass parts deionized waters and mixed, then add 7 mass parts elemental sulfur powder and 2 mass parts carbon blacks, mix and obtain slurry, gained slurry is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm again
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 2
95 mass parts gelatinized starches and 5 mass parts polyvinyl alcohol are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is added in 300 mass parts deionized waters, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally gained slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 3
50 mass parts gelatinized starches and 50 mass parts sodium cellulose glycolates are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts distilled water, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 4
50 mass parts gelatinized starches, 10 mass parts polyvinyl alcohol and 40 mass parts sodium cellulose glycolates are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts deionized waters, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 5
50 mass parts gelatinized starches, 40 mass parts polyvinyl alcohol and 10 mass parts sodium cellulose glycolates are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts deionized waters, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 6
95 mass parts gelatinized starches and 5 mass parts sodium cellulose glycolates are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts distilled water, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 7
95 mass parts gelatinized starches, 4 mass parts polyvinyl alcohol and 1 mass parts sodium cellulose glycolate are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts deionized waters, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
70 mass parts gelatinized starches, 24 mass parts polyvinyl alcohol and 6 mass parts sodium cellulose glycolates are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts deionized waters, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 9
70 mass parts gelatinized starches, 6 mass parts polyvinyl alcohol and 24 mass parts sodium cellulose glycolates are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts deionized waters, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 10
85 mass parts gelatinized starches, 12 mass parts polyvinyl alcohol and 3 mass parts sodium cellulose glycolates are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts deionized waters, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 11
85 mass parts gelatinized starches, 3 mass parts polyvinyl alcohol, 12 mass parts sodium cellulose glycolates are added to be ground to mix in mortar and obtain lithium-sulphur cell positive electrode binding agent, then described binding agent is joined in 300 mass parts deionized waters, mix, add again 700 mass parts elemental sulfur powder and 200 mass parts carbon blacks, mix and obtain slip, finally described slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Comparative example
Kynoar is current the most frequently used lithium-sulphur cell positive electrode binding agent, so this comparative example adopts Kynoar to carry out comparative study as binding agent.
1 mass parts Kynoar is dissolved in 50 mass parts 1-METHYLPYRROLIDONEs and forms binder solution, then add 7 mass parts elemental sulfur powder and 2 mass parts carbon blacks, mix and obtain slip, then slip is evenly coated on aluminium foil, during coating, on aluminium foil, the load capacity of elemental sulfur powder is 1mg/cm
2, finally at normal pressure, the air drying 24h of 60 ℃, obtain the positive pole of lithium-sulfur cell.
The positive pole preparing, lithium paper tinsel negative pole, barrier film and electrolyte in being less than the argon gas glove box of 10ppm, water content are assembled into button cell; Described electrolyte is the glycol dimethyl ether of bis trifluoromethyl Sulfonic Lithium and the mixed solution of 1,3 dioxolanes that contains 0.65mol/L, and the volume ratio of glycol dimethyl ether and 1,3 dioxolanes is 1:1.
Embodiment 12: performance test
The button cell of preparing in embodiment 1～embodiment 11 and comparative example is tested on Land2001A cell tester, test mode is constant current charge-discharge, and cut-ff voltage is 1.0～3.0V, and measuring current is 0.2C(334mA/g), probe temperature is room temperature, and cycle-index is 100 times.
Fig. 1～Figure 11 is respectively the cycle performance figure of lithium-sulfur cell prepared by embodiment 1～embodiment 11 and comparative example, from Fig. 1～Figure 11, adopts the cycle performance of lithium-sulfur cell prepared by the binding agent of formula of the present invention to be greatly improved.The capability retention that the lithium-sulfur cell of embodiment 1～embodiment 11 preparations circulates after 100 times under 0.2C current density is respectively 63%, 65%, 73%, 73%, 70%, 76%, 81%, 83%, 94%, 96% and 96%, and the capability retention of lithium-sulfur cell prepared by comparative example is only 34%, show that binding agent of the present invention is very outstanding in the performance of improving aspect lithium-sulfur cell cycle performance.
Claims (7)
1. a lithium-sulphur cell positive electrode binding agent, is characterized in that this binding agent comprises gelatinized starch.
2. lithium-sulphur cell positive electrode binding agent according to claim 1, is characterized in that described binding agent is comprised of the gelatinized starch of 50～95wt% and the additive of 50～5wt%.
3. lithium-sulphur cell positive electrode binding agent according to claim 2, is characterized in that described additive is at least one in sodium cellulose glycolate or polyvinyl alcohol.
4. lithium-sulphur cell positive electrode binding agent according to claim 3, is characterized in that described binding agent is comprised of the gelatinized starch of 70～95wt% and the additive of 30～5wt%.
5. lithium-sulphur cell positive electrode binding agent according to claim 4, is characterized in that described binding agent is comprised of the gelatinized starch of 85～95wt% and the additive of 15～5wt%.
6. according to lithium-sulphur cell positive electrode binding agent described in any one claim in claim 3 to 5, it is characterized in that when described additive is sodium cellulose glycolate and polyvinyl alcohol, the mass ratio of sodium cellulose glycolate and polyvinyl alcohol is 1:4～4:1.
7. lithium-sulphur cell positive electrode application in lithium-sulfur cell preparation with binding agent described in any one claim in claim 1 to 6.
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| CN107887569A (en) * | 2017-10-27 | 2018-04-06 | 惠州拓邦电气技术有限公司 | A kind of lithium ion battery cathode slurry and preparation method thereof |
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| CN103985902A (en) * | 2014-05-30 | 2014-08-13 | 北京理工大学 | Method for improving performance of lithium sulfur battery by utilizing desolvation colloidal electrolyte |
| CN108155383A (en) * | 2017-11-29 | 2018-06-12 | 中山大学 | A kind of lithium-sulfur cell binding agent and preparation method thereof and lithium-sulphur cell positive electrode |
| CN108155383B (en) * | 2017-11-29 | 2020-07-28 | 中山大学 | Binder for lithium-sulfur battery, preparation method of binder and lithium-sulfur battery anode |
| CN109337607A (en) * | 2018-09-29 | 2019-02-15 | 安徽兆拓新能源科技有限公司 | A kind of high-performance composite adhesive and photovoltaic back |
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| CN109337592A (en) * | 2018-10-18 | 2019-02-15 | 合肥永泰新型建材有限公司 | A kind of compound adhesive of heat-proof aging freeze thawing |
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| CN111554930A (en) * | 2020-05-08 | 2020-08-18 | 珠海冠宇电池股份有限公司 | Binder and lithium ion battery containing same |
| CN111554930B (en) * | 2020-05-08 | 2021-08-27 | 珠海冠宇电池股份有限公司 | Binder and lithium ion battery containing same |
| WO2024050810A1 (en) * | 2022-09-09 | 2024-03-14 | 宁德时代新能源科技股份有限公司 | Binder composition and electrode sheet prepared from same |
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