CN109167104A - A kind of room temperature sodium-sulphur battery and preparation method thereof - Google Patents

A kind of room temperature sodium-sulphur battery and preparation method thereof Download PDF

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Publication number
CN109167104A
CN109167104A CN201811061144.2A CN201811061144A CN109167104A CN 109167104 A CN109167104 A CN 109167104A CN 201811061144 A CN201811061144 A CN 201811061144A CN 109167104 A CN109167104 A CN 109167104A
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Prior art keywords
sodium
room temperature
solid electrolyte
sulphur battery
sulphur
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CN201811061144.2A
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Chinese (zh)
Inventor
朱业
王玉虎
程君
孙文坡
全家岸
徐雪菲
贾明杰
丁超
韩天鑫
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Lixin Jiangsu Energy Technology Co Ltd
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Lixin Jiangsu Energy Technology Co Ltd
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Priority to CN201811061144.2A priority Critical patent/CN109167104A/en
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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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a kind of room temperature sodium-sulphur batteries and preparation method thereof, positive plate and negative electrode tab are separated by solid electrolyte, and between positive plate and solid electrolyte, be designed with liquid electrolyte between negative electrode tab and solid electrolyte and be prepared into room temperature sodium-sulphur battery, the use of solid electrolyte, the shuttle effect of polysulfide can effectively be avoided, liquid electrolyte on positive/negative plate and solid electrolyte contact surface simultaneously, the impedance between pole piece and solid electrolyte interface is effectively reduced, improves the high rate performance of battery；Furthermore the sodium-sulphur battery can work at normal temperature, enhance the safety of battery, reduce security risk probability of happening；The sodium-sulphur battery that the present invention prepares also has low cost, long circulating, low energy consumption, high stability, environment friendly and pollution-free advantage.

Description

A kind of room temperature sodium-sulphur battery and preparation method thereof
Technical field
The present invention relates to the preparation fields of lithium ion battery more particularly to a kind of room temperature sodium-sulphur battery and preparation method thereof.
Background technique
In recent years, with electrified development, the dependence to electric power of people is more and more important, and the demand of power grid energy storage is got over Come bigger.The advantages that sodium-sulphur battery is a kind of new secondary battery, has small in size, and capacity is big, and the service life is long, high-efficient.And The positive and negative anodes sodium and sulphur of the battery are from a wealth of sources, environmental-friendly, low-cost materials.Sodium-sulphur battery is in energy storage at present The use of commercial scale is obtained on field.
But commercialized sodium-sulphur battery remains some serious defects at present.Sodium commercially use at present Sulphur battery is the high temperature sodium-sulphur battery, due under room temperature, conventional solid positive and negative anodes and βAl2O3 (β-Al2O3) solid electrolyte Ion conductance is lower, only when temperature need to be up to 300-350 DEG C, after positive sulphur and cathode sodium become molten state, positive and negative anodes with And βAl2O3 ability ion conductance with higher, sodium-sulphur battery could work normally at this time.Sodium-sulphur battery operating temperature is maintained to need A large amount of energy consumption is wanted, and high temperature proposes challenge to the safety of sodium-sulphur battery.
Therefore, prepare it is a kind of can the sodium-sulphur battery that uses of room temperature there is great scientific research value and commercial value.
Summary of the invention
Goal of the invention: in order to overcome defect existing in the prior art, the invention proposes a kind of room temperature sodium-sulphur battery and Preparation method, work use under normal temperature conditions, and preparation process is simple, and materials are low in cost, and battery has long circulating, high The advantages of stability, environmental pollution, and security performance is high, reduces security risk probability of happening.
Technical solution: in order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is as follows: a kind of room temperature sodium sulphur electricity Pond, including positive plate, negative electrode tab, solid electrolyte；The solid electrolyte separates positive plate and negative electrode tab, the positive plate Liquid electrolyte is designed between solid electrolyte, between the negative electrode tab and solid electrolyte.
Using solid electrolyte, the shuttle effect of polysulfide, while positive/negative plate and solid electrolytic can be effectively avoided The impedance between pole piece and solid electrolyte interface is effectively reduced in liquid electrolyte on matter contact surface, improves the forthright again of battery Energy.
More preferably, the positive plate includes positive active material, plus plate current-collecting body, binder and conductive agent.
Further, the positive active material be one of elemental sulfur, sulphur/porous carbon mix, vulcanized sodium or It is a variety of.
Further, the plus plate current-collecting body is smooth surface aluminium foil, in utter misery aluminium foil, porous aluminium foil, porous utter misery aluminium foil One kind.
Further, the binder is Kynoar, butadiene-styrene rubber and sodium carboxymethylcellulose mixture, carboxylic first At least one of base sodium cellulosate, polyacrylic acid, sodium alginate.
Further, the conductive agent is conductive black, electrically conductive graphite, one of graphene or carbon nanotube or several Kind mixing.
Further, the solid electrolyte includes sodium superionic conductors series NASICON, sodium tin phosphorus sulphur NSPS, boron Sodium hydride NaBH4, sodium amide NaNH2, sodium borohydride and sodium amide mixture Na (BH4)X(NH2)(1-X)One of or A variety of mixing
More preferably, the liquid electrolyte is using traditional ethers electrolyte as solvent, with sodium perchlorate, hexafluorophosphoric acid Sodium, one or more of double trifluoromethanesulfonimide sodium are used as solute, vulcanized sodium or sodium polysulfide be additive prepare and At.
Further, traditional ethers electrolyte includes 1,3-dioxolane, dimethyl ether, tetrahydrofuran, ethylene glycol Dimethyl ether, diethylene glycol dimethyl ether, one of triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether or a variety of mixed It closes.
The invention also discloses the preparation methods of above-mentioned room temperature sodium-sulphur battery, include the following steps:
(1) preparation of positive plate: by positive active material and binder, conductive agent mixed pulp, it is coated in anode collection On body, it is prepared after drying；
(2) negative electrode tab is prepared using metallic sodium；
(3) solid electrolyte is by sodium superionic conductors series NASICON, sodium tin phosphorus sulphur NSPS, sodium borohydride NaBH4, ammonia Base sodium NaNH2, sodium borohydride and sodium amide mixture Na (BH4)X(NH2)(1-X)One of or a variety of be mixed with and At.
(4) preparation of liquid electrolyte: using traditional ethers electrolyte as solvent, with sodium perchlorate, sodium hexafluoro phosphate is double One or more of trifluoromethanesulfonimide sodium is used as solute, and vulcanized sodium or sodium polysulfide are prepared for additive；
(5) preparation is successively superimposed by the sequence of positive plate, liquid electrolyte, solid electrolyte, liquid electrolyte, negative electrode tab At room temperature sodium-sulphur battery, wherein the additive amount control of liquid electrolyte is to infiltrate connecing for positive plate or negative electrode tab and solid electrolyte Contacting surface.
The utility model has the advantages that a kind of room temperature sodium-sulphur battery provided by the invention and preparation method thereof, has the advantage that (1) is adopted With solid electrolyte, the shuttle effect of polysulfide can be effectively avoided, while on positive/negative plate and solid electrolyte contact surface Liquid electrolyte, the impedance between pole piece and solid electrolyte interface is effectively reduced, improves the high rate performance of battery；(2) can It works at normal temperature, enhances battery security, reduce security risk probability of happening；(3) sodium-sulphur battery prepared have it is low at This, long circulating, low energy consumption, high stability, environment friendly and pollution-free advantage.
Detailed description of the invention
Fig. 1 is the structural schematic diagram that the present invention uses 1 room temperature sodium-sulphur battery of embodiment；
Fig. 2 is the structural schematic diagram of traditional sodium-sulphur battery；
Fig. 3 follows for the room temperature charge-discharge performance of 1 room temperature sodium-sulphur battery of the embodiment of the present invention and comparative example tradition sodium-sulphur battery Ring test contrast schematic diagram.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail:
It please refers to shown in Fig. 1, the room temperature sodium-sulphur battery of embodiment 1- embodiment 2 includes positive plate 1, negative electrode tab 2, solid electricity Solve matter 3；The solid electrolyte 3 separates positive plate 1 and negative electrode tab 2, between the positive plate 1 and solid electrolyte 3, described Liquid electrolyte 4 is designed between negative electrode tab 2 and solid electrolyte 3.
Embodiment 1:
A kind of preparation method of room temperature sodium-sulphur battery, includes the following steps:
(1) preparation of positive plate: elemental sulfur is uniformly mixed with porous carbon with the mass ratio of 6:4, is heated to 155 DEG C of heat preservations 10h is prepared into solid mixture, and the solid mixture being prepared grinding crushed into powder is obtained sulphur/porous carbon mix, will Sulphur/porous carbon mix is 7:2:1 according to mass ratio with conductive carbon black (SP), Kynoar (PVDF), with N-methyl pyrroles Alkanone (NMP) is after solvent grinds slurrying, mixed slurry to be coated on the porous utter misery aluminium foil that aperture is 250 μm, after drying It is prepared into positive plate；
(2) negative electrode tab is prepared using metallic sodium；Solid electrolyte is using one of sodium superionic conductors series Na3Zr2Si2PO12；
(3) preparation of liquid electrolyte: with 1,3- dioxolane and glycol dimethyl ether with volume ratio 1:1 mixing do it is molten Agent, the double trifluoromethanesulfonimide sodium for adding 1mol/L are solute, then add 2% vulcanized sodium (Na2S it) is prepared as additive It forms；
(4) preparation is successively superimposed by the sequence of positive plate, liquid electrolyte, solid electrolyte, liquid electrolyte, negative electrode tab At room temperature sodium-sulphur battery；Wherein the preparation of solid electrolyte is with a thickness of 50 μm；The additive amount of liquid electrolyte is controlled to infiltrate just The contact surface of pole piece or negative electrode tab and solid electrolyte.
Embodiment 2:
A kind of preparation method of room temperature sodium-sulphur battery, includes the following steps:
(1) preparation of positive plate: by simple substance small molecule sulphur and carbon nanotube (CNT), polyacrylic acid (PAA) according to mass ratio For 8:1:1, grinding slurrying is taken water as a solvent, is coated on utter misery aluminium foil, is prepared into positive plate after the drying；
(2) negative electrode tab is prepared using metallic sodium；Solid electrolyte uses the mixture of sodium borohydride and sodium amide One of (Na (BH4)0.5(NH2)0.5)；
(3) preparation of liquid electrolyte: solvent is done with volume ratio 1:1 mixing with 1,3- dioxolane and tetrahydrofuran, is added The sodium perchlorate for adding 1mol/L is solute, then adds 2% vulcanized sodium (Na2S it) is prepared as additive；
(4) preparation is successively superimposed by the sequence of positive plate, liquid electrolyte, solid electrolyte, liquid electrolyte, negative electrode tab At room temperature sodium-sulphur battery；Wherein the preparation of solid electrolyte is with a thickness of 40 μm；The additive amount of liquid electrolyte is controlled to infiltrate just The contact surface of pole piece or negative electrode tab and solid electrolyte.
Comparative example:
Routine business sodium-sulphur battery works at high temperature, and is anode with the sulphur simple substance under molten condition, with molten state simple substance Sodium is cathode, with βAl2O3 (β-Al2O3) it is used as diaphragm and solid electrolyte, no liquid electrolyte.It please refers to shown in Fig. 2, is The structural schematic diagram of routine business sodium-sulphur battery.
Test method:
Test object is the routine business sodium-sulphur battery of room temperature sodium-sulphur battery prepared by embodiment 1 and comparative example.
Cyclic charging and discharging test under room temperature:
Sodium-sulphur battery prepared by embodiment 1 and comparative example is filled under 25 DEG C ± 10 DEG C of environment temperature with 0.5C/0.5C Discharge-rate carries out charge and discharge cycles in 1.78-2.21V voltage range and records circulating ring number and capacity attenuation rate, as a result remembers Record is as shown in Figure 3.
Please refer to the room temperature charge-discharge performance loop test schematic diagram of the sodium-sulphur battery of Fig. 3 embodiment 1 and comparative example preparation； , it is apparent that the room temperature sodium-sulphur battery of embodiment 1 still keeps 100% height after circulating ring number 1500 times under normal temperature conditions Capacity retention ratio, and traditional sodium-sulphur battery of comparative example can not work under normal temperature conditions.

Claims (10)

1. a kind of room temperature sodium-sulphur battery, it is characterised in that including positive plate (1), negative electrode tab (2), solid electrolyte (3)；It is described solid Body electrolyte (3) separates positive plate (1) and negative electrode tab (2), between the positive plate (1) and solid electrolyte (3), described negative Liquid electrolyte (4) are designed between pole piece (2) and solid electrolyte (3).
2. room temperature sodium-sulphur battery according to claim 1, it is characterised in that: the positive plate (1) includes positive electrode active material Matter, plus plate current-collecting body, binder and conductive agent.
3. room temperature sodium-sulphur battery according to claim 2, it is characterised in that: the positive active material be elemental sulfur, sulphur/ One of porous carbon mix, vulcanized sodium are a variety of.
4. room temperature sodium-sulphur battery according to claim 2, it is characterised in that: the plus plate current-collecting body is smooth surface aluminium foil, applies One of charcoal aluminium foil, porous aluminium foil, porous utter misery aluminium foil.
5. room temperature sodium-sulphur battery according to claim 2, it is characterised in that: the binder is Kynoar, butylbenzene Rubber and at least one of sodium carboxymethylcellulose mixture, sodium carboxymethylcellulose, polyacrylic acid, sodium alginate.
6. room temperature sodium-sulphur battery according to claim 2, it is characterised in that: the conductive agent be conductive black, electrically conductive graphite, The mixing of one or more of graphene or carbon nanotube.
7. room temperature sodium-sulphur battery according to claim 1, it is characterised in that: the solid electrolyte (3) include sodium surpass from Sub- conductor series NASICON, sodium tin phosphorus sulphur NSPS, sodium borohydride NaBH4, sodium amide NaNH2, sodium borohydride and sodium amide Mixture Na (BH4)X(NH2)(1-X)One of or a variety of mixing.
8. room temperature sodium-sulphur battery according to claim 1, it is characterised in that: the liquid electrolyte (4) is with traditional ethers Electrolyte is as solvent, and with sodium perchlorate, sodium hexafluoro phosphate, one or more of double trifluoromethanesulfonimide sodium are as molten Matter, vulcanized sodium or sodium polysulfide are prepared for additive.
9. room temperature sodium-sulphur battery according to claim 8, it is characterised in that: the tradition ethers electrolyte includes 1,3- bis- Butyl oxide link, dimethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetrem One of glycol dimethylether or a variety of mixing.
10. a kind of preparation method of room temperature sodium-sulphur battery described in claim 1, it is characterised in that include the following steps:
(1) preparation of positive plate: positive active material and binder, conductive agent mixed pulp are coated on plus plate current-collecting body, It is prepared after drying；
(2) negative electrode tab is prepared using metallic sodium；
(3) solid electrolyte is by sodium superionic conductors series (NASICON), sodium tin phosphorus sulphur (NSPS), sodium borohydride NaBH4, amino Change sodium NaNH2, sodium borohydride and sodium amide mixture (Na (BH4)X(NH2)(1-X)) one of or a variety of be mixed with and At.
(4) preparation of liquid electrolyte: using traditional ethers electrolyte as solvent, with sodium perchlorate, sodium hexafluoro phosphate, double trifluoros One or more of sulfonyl methane imines sodium is used as solute, and vulcanized sodium or sodium polysulfide are prepared for additive；
(5) by positive plate, liquid electrolyte, solid electrolyte, liquid electrolyte, negative electrode tab sequence be successively superimposed be prepared into often Warm sodium-sulphur battery, wherein the additive amount of liquid electrolyte is controlled to infiltrate the contact surface of positive plate or negative electrode tab and solid electrolyte ?.
CN201811061144.2A 2018-09-12 2018-09-12 A kind of room temperature sodium-sulphur battery and preparation method thereof Pending CN109167104A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110649314A (en) * 2019-09-24 2020-01-03 广东天劲新能源科技股份有限公司 All-solid-state sodium-sulfur battery and preparation method thereof
CN112002934A (en) * 2020-08-31 2020-11-27 大连理工大学 Rechargeable sulfur ion battery and preparation method thereof
CN112993244A (en) * 2021-02-07 2021-06-18 广东工业大学 Room-temperature full-liquid-state lithium-sulfur battery and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103531840A (en) * 2013-11-01 2014-01-22 中国科学院上海硅酸盐研究所 Double-electrolyte system lithium sulphur battery and preparing method thereof
CN105374980A (en) * 2014-08-15 2016-03-02 中国科学院物理研究所 An interface infiltrated quasi-solid alkali metal cell, electrodes of the cell and a preparing method of the cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103531840A (en) * 2013-11-01 2014-01-22 中国科学院上海硅酸盐研究所 Double-electrolyte system lithium sulphur battery and preparing method thereof
CN105374980A (en) * 2014-08-15 2016-03-02 中国科学院物理研究所 An interface infiltrated quasi-solid alkali metal cell, electrodes of the cell and a preparing method of the cell

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110649314A (en) * 2019-09-24 2020-01-03 广东天劲新能源科技股份有限公司 All-solid-state sodium-sulfur battery and preparation method thereof
CN112002934A (en) * 2020-08-31 2020-11-27 大连理工大学 Rechargeable sulfur ion battery and preparation method thereof
CN112002934B (en) * 2020-08-31 2024-02-06 大连理工大学 Rechargeable sulfur ion battery and preparation method thereof
CN112993244A (en) * 2021-02-07 2021-06-18 广东工业大学 Room-temperature full-liquid-state lithium-sulfur battery and preparation method thereof

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