CN105489895A - Conductive paste for lithium-sulfur battery, preparation method of conductive paste and preparation method of positive sulfur electrode plate of lithium-sulfur battery - Google Patents
Conductive paste for lithium-sulfur battery, preparation method of conductive paste and preparation method of positive sulfur electrode plate of lithium-sulfur battery Download PDFInfo
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- CN105489895A CN105489895A CN201510827993.4A CN201510827993A CN105489895A CN 105489895 A CN105489895 A CN 105489895A CN 201510827993 A CN201510827993 A CN 201510827993A CN 105489895 A CN105489895 A CN 105489895A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/625—Carbon or graphite
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a conductive paste for a lithium-sulfur battery. The conductive paste is prepared from the following components in parts by weight: 2 parts of tragacanth gum, 35-40 parts of water, 4-8 parts of elemental sulfur and 2-6 parts of KS-6, wherein the tragacanth gum is secretion of astragalus gummifera; the viscosity of the solution of the tragacanth gum is the highest in gum; and the tragacanth gum is mainly applied to food, medicines and cosmetics, but application of the tragacanth gum in preparation of the battery is not expected. A research shows that with the tragacanth gum as a positive material binder for a lithium-sulfur rechargeable battery, the electrochemical properties of the electrode material are improved; and the tragacanth gum is free of pollution to environment and free of an injury to a human body. Through a test, the cycle index of the lithium-sulfur battery made of the positive material is greater than 200 at a high discharge specific capacitance (1200mAh/g); and the capacitance can still be kept stable. The KS-6 is large-particle graphite powder, is in a feather shape, has a certain lithium storage function and is applied to a positive electrode in practical production. The KS-6 conductive agent is coordinated with the tragacanth gum, so that the electrical properties are not easily reduced after sulfur is doped; and excellent electrochemical properties can still be kept when the sulfur-carbon ratio reaches 4 to 1.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode material, more particularly, is a kind of modified sulphur electrode material.
Background technology
It is high that lithium ion battery has energy density, the advantages such as self discharge is little, memory-less effect, operating temperature range are wide, have extended cycle life, be the better secondary cell system of current combination property, and be widely used on the portable electric appts such as mobile phone, digital camera and notebook computer.But along with the development of electronic electric equipment, the rise of electric automobile and hybrid vehicle especially in recent years, conventional lithium ion battery has more and more been difficult to meet the demand of people for the energy content of battery.Conventional lithium ion battery positive electrode based on transition metal oxide (as LiCoO
2, LiMnO
2and LiFePO
4deng), although have advantages such as having extended cycle life, fail safe is good, be subject to the restriction of its relatively low theoretical specific capacity, be difficult to meet the demand of electrokinetic cell to high-energy-density.Lithium-sulfur cell take elemental sulfur as positive pole, and lithium metal is the battery system of negative pole.Elemental sulfur has 1675mAhg
-1theoretical specific capacity, corresponding lithium-sulfur cell has 2600Whkg
-1theoretical specific energy, it is nearly about 10 times that current commercial Li-ion battery reality can reach, the wide material sources of active material sulphur, cheap simultaneously, environmental friendliness, therefore lithium-sulfur cell is considered to one of most potentiality a new generation high energy energy storage system (see Manthiram, A., S.H.Chung, andC.Zu, Lithium-sulfurbatteries:progressandprospects [J] .AdvMater, 2015.27 (12): 1980-2006.).Although lithium-sulfur cell has so tempting advantage, this system still also exists some problems, causes its commercialization process slow.These problems comprise sulphur and reduzate Li
2electronics, the ionic conductivity of S are poor, charge and discharge process electrode change in volume is large, intermediate product in the electrolytic solution there is dissolubility and adjoint " effect of shuttling back and forth " etc., cause the cycle life of lithium-sulfur cell poor (see Fang, X.andH.Peng, Arevolutioninelectrodes:recentprogressinrechargeablelith ium-sulfurbatteries [J] .Small, 2015.11 (13): 1488-511.).In recent years, all kinds of sulphur carbon composite material is synthesized, and effectively improve the chemical property of lithium-sulfur cell, then the complicated and special construction material with carbon element of costliness is prepared and is not suitable for suitability for industrialized production, and adopts multifunctional binder to be expected to simply and effectively reach the object promoting battery performance.In the battery, binding agent is generally be bonded on collector by active material, is used to the structural intergrity of maintenance electrode, guarantees electronics path in charge and discharge process, ensureing the macromolecular material that battery normally runs, is the vital factor affecting battery performance.The present binding agent for lithium sulfur battery anode material is still based on traditional Kynoar (PVDF).But traditional Kynoar is as binding agent, because its toxicity is excessive, and poisonous solvent must be used, very large to the pollution of environment in production, the health of operating personnel is threatened.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of cheap, safety and environmental protection, be easy to industrialization, the lithium-sulfur cell electrocondution slurry of sulphur positive pole chemical property can be significantly improved;
Another object of the present invention is to provide the preparation method of above-mentioned lithium-sulfur cell sulphur anode sizing agent;
Another object of the present invention is to provide and above-mentionedly utilizes above-mentioned lithium-sulphur cell positive electrode slurry to prepare lithium-sulphur cell positive electrode electrode slice.
A kind of lithium-sulfur cell electrocondution slurry, each component comprises by weight: bassora gum 2 parts, water 35-40 part, elemental sulfur 4-8 part, KS-62-6 part.
Preferably, above-mentioned lithium-sulfur cell electrocondution slurry, each component comprises by weight: bassora gum 2 parts, 36 parts, water, elemental sulfur 6 parts, KS-63 part.
Preferably, described elemental sulfur is sublimed sulfur.
Preferably, described water is deionized water.
The preparation method of above-mentioned lithium-sulfur cell electrocondution slurry, is added to the water dissolving dispersion by formula rate by bassora gum, adds elemental sulfur and KS-6, be stirred to and mix.
A preparation method for lithium-sulfur cell sulphur anode electrode sheet, comprises the steps:
1) aluminium foil is cleaned with deionized water and acetone successively, dry, to be cut into diameter 14mm disk;
2) be poured on the aluminium foil after cleaning-drying by above-mentioned slurry, by the mode of spin coating, slurry be coated in the hair side of aluminium foil, after dry, cooling, can obtain anode electrode sheet.
Preferably, described step 1) in, described cutting adopts the mode of 80 DEG C of lower die cut.
Preferably, described step 2) in, the process of described drying adopts the method for first vacuumize constant pressure and dry again.
Preferred further, described vacuum drying temperature is 60 DEG C, drying time is 8h; The temperature of described constant pressure and dry is 80 DEG C, drying time is 2h.
Preferably, described step 2) in, described cooling procedure adopts and is cooled rapidly in 30s by dried electrode slice.
Preferably, described step 2) in, 2ml slurry is spun on the aluminium foil of 14mm uniformly.
Bassora gum is the secretion of tragacantha shrub tree.The viscosity of the solution with it in natural gum is the highest, is mainly used in food, medicine and cosmetics, but nobody expects being applied in the preparation of battery.The present invention finds after deliberation, utilizes bassora gum as the agent of lithium-sulfur rechargeable battery anode material binding, not only increases the chemical property of electrode material, and to environment without any pollution, is injury to human body.After tested, the lithium-sulfur cell of positive electrode of the present invention is when height discharges ratio capacitance (1200mAh/g), and cycle-index is more than 200 times, and electric capacity still can keep stable.
KS-6 is bulky grain graphite powder, featheriness, has certain storage lithium function, for positive pole in actual production.The present invention is by KS-6 conductive agent, and bassora gum is worked in coordination with, and after mixing sulphur, its electric conductivity is not easy to decline, and sulphur carbon ratio reaches the chemical property that 4:1 still keeps excellent.When sulphur carbon ratio is 2:1, the electricity voltinism energy of battery the best can be realized.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Embodiment 1:
A kind of lithium-sulfur cell electrocondution slurry, each component and content are see table 1.
Its preparation method is, by formula rate, bassora gum is added to the water dissolving dispersion, adds elemental sulfur and KS-6, be stirred to and mix.
Be prepared into lithium-sulfur cell sulphur anode electrode sheet further, comprised the steps:
1) aluminium foil is cleaned with deionized water and acetone successively, the disk dry, 80 DEG C of counterdies are cut into diameter 14mm;
2) above-mentioned slurry is poured on the aluminium foil after cleaning-drying, 2ml slurry is spun on uniformly the hair side of aluminium foil, first vacuumize, temperature is 60 DEG C, drying time is 8h, constant pressure and dry again, temperature is 80 DEG C, drying time is be cooled to room temperature rapidly in 2h, 30s, can obtain anode electrode sheet.
Adopt the lithium-sulfur cell the performance test results of this enforcement electrode slice see table 1.
Embodiment 2:
A kind of lithium-sulfur cell electrocondution slurry, each component and content are see table 1.
Its preparation method is with embodiment 1.
Make the method for electrode slice with embodiment 1.
Adopt the lithium-sulfur cell the performance test results of this enforcement electrode slice see table 1.
Embodiment 3:
A kind of lithium-sulfur cell electrocondution slurry, each component and content are see table 1.
Its preparation method is with embodiment 1.
Make the method for electrode slice with embodiment 1.
Adopt the lithium-sulfur cell the performance test results of this enforcement electrode slice see table 1.
Embodiment 4:
A kind of lithium-sulfur cell electrocondution slurry, each component and content are see table 1.
Its preparation method is with embodiment 1.
Make the method for electrode slice with embodiment 1.
Adopt the lithium-sulfur cell the performance test results of this enforcement electrode slice see table 1.
Table 1
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a lithium-sulfur cell electrocondution slurry, is characterized in that: each component comprises by weight: bassora gum 2 parts, water 35-40 part, elemental sulfur 4-8 part, KS-62-6 part.
2. lithium-sulfur cell electrocondution slurry according to claim 1, is characterized in that: each component comprises by weight: bassora gum 2 parts, 36 parts, water, elemental sulfur 6 parts, KS-63 part.
3. lithium-sulfur cell electrocondution slurry according to claim 1 and 2, is characterized in that: described elemental sulfur is sublimed sulfur.
4. modification lithium-sulfur cell sulphur positive pole nano pulp according to claim 1 and 2, is characterized in that: described water is deionized water.
5. the preparation method of the lithium-sulfur cell electrocondution slurry according to any one of Claims 1-4, is characterized in that: by formula rate, bassora gum is added to the water dissolving dispersion, adds elemental sulfur and KS-6, be stirred to and mix.
6. a preparation method for lithium-sulfur cell sulphur anode electrode sheet, is characterized in that: comprise the steps:
1) aluminium foil is cleaned with deionized water and acetone successively, dry, be cut into the disk of diameter 14mm;
2) slurry described in any one of claim 1-4 is poured on the aluminium foil after cleaning-drying, by the mode of spin coating, slurry is coated in the hair side of aluminium foil, is cooled to room temperature after drying, anode electrode sheet can be obtained.
7. the preparation method of lithium-sulfur cell sulphur anode electrode sheet according to claim 6, is characterized in that: described step 1) in, described cutting adopts the mode of 80 DEG C of lower die cut.
8. the preparation method of lithium-sulfur cell sulphur anode electrode sheet according to claim 6, is characterized in that: described step 2) in, the process of described drying adopts the method for first vacuumize constant pressure and dry again; Described cooling procedure adopts and is cooled rapidly in 30s by dried electrode slice.
9. the preparation method of lithium-sulfur cell sulphur anode electrode sheet according to claim 8, is characterized in that: described vacuum drying temperature is 60 DEG C, drying time is 8h; The temperature of described constant pressure and dry is 80 DEG C, drying time is 2h.
10. the preparation method of lithium-sulfur cell sulphur anode electrode sheet according to claim 6, is characterized in that: described step 2) in, 2ml slurry is spun on the aluminium foil of 14mm uniformly.
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| CN201510827993.4A CN105489895A (en) | 2015-11-24 | 2015-11-24 | Conductive paste for lithium-sulfur battery, preparation method of conductive paste and preparation method of positive sulfur electrode plate of lithium-sulfur battery |
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| CN201510827993.4A CN105489895A (en) | 2015-11-24 | 2015-11-24 | Conductive paste for lithium-sulfur battery, preparation method of conductive paste and preparation method of positive sulfur electrode plate of lithium-sulfur battery |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112117447A (en) * | 2020-09-23 | 2020-12-22 | 金汤杰 | Preparation process of composite lithium battery negative electrode material |
| CN112898949A (en) * | 2021-01-19 | 2021-06-04 | 华南农业大学 | Lithium-sulfur battery containing plant juice-based binder |
Citations (2)
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| CN1333576A (en) * | 2000-03-13 | 2002-01-30 | 佳能株式会社 | Electrode material for rechargeable lithium cell, electrod structure body, cell, and production method thereof |
| CN101924200A (en) * | 2010-09-02 | 2010-12-22 | 上海交通大学 | Application of adhesive to lithium-sulfur rechargeable battery anode |
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2015
- 2015-11-24 CN CN201510827993.4A patent/CN105489895A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333576A (en) * | 2000-03-13 | 2002-01-30 | 佳能株式会社 | Electrode material for rechargeable lithium cell, electrod structure body, cell, and production method thereof |
| CN101924200A (en) * | 2010-09-02 | 2010-12-22 | 上海交通大学 | Application of adhesive to lithium-sulfur rechargeable battery anode |
Non-Patent Citations (1)
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| 张倩: "《三维结构基底负载硅薄膜负极材料的制备及性能研究》", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112117447A (en) * | 2020-09-23 | 2020-12-22 | 金汤杰 | Preparation process of composite lithium battery negative electrode material |
| CN112898949A (en) * | 2021-01-19 | 2021-06-04 | 华南农业大学 | Lithium-sulfur battery containing plant juice-based binder |
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Application publication date: 20160413 |