CN106532012B - A kind of sulphur-biomass carbon/transition metal combination electrode material and its preparation method and application - Google Patents

A kind of sulphur-biomass carbon/transition metal combination electrode material and its preparation method and application Download PDF

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CN106532012B
CN106532012B CN201611205892.4A CN201611205892A CN106532012B CN 106532012 B CN106532012 B CN 106532012B CN 201611205892 A CN201611205892 A CN 201611205892A CN 106532012 B CN106532012 B CN 106532012B
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transition metal
sulphur
biomass carbon
combination electrode
nitrate
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CN201611205892.4A
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CN106532012A (en
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夏新辉
钟宇
詹继烨
涂江平
王秀丽
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浙江大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of sulphur-biomass carbon/transition metal combination electrode materials and its preparation method and application, pass through extruding, it impregnates, high temperature method generates biomass carbon/transition metal composite material, as carrier after reaction, pass through sulfurizing method, reaction 12~18 hours, the compounding simple-substance sulphur in biomass carbon/transition metal composite material prepares lithium-sulfur cell sulphur-biomass carbon/transition metal combination electrode material.Sulphur-biomass carbon/transition metal combination electrode material of the present invention has height ratio capacity, high rate capability and high circulation service life, particularly suitable for preparing the anode of lithium-sulfur cell, have broad application prospects in fields such as mobile communication, electric car, solar power generation and aerospaces.

Description

A kind of sulphur-biomass carbon/transition metal combination electrode material and preparation method thereof and Using
Technical field
The present invention relates to lithium-sulfur cell composite anode materials technical fields, and in particular to a kind of sulphur-biomass carbon/transition gold Belong to combination electrode material and preparation method thereof and the application in the anode for preparing lithium-sulfur cell.
Background technique
With gradually using up totally for fossil energy, and the greenhouse effects and problem of environmental pollution that thus cause, the mankind There is an urgent need to develop renewable and clean energy resource.It in recent years, is the secondary cell of representative as a kind of high-performance using lithium ion battery Electrochemical energy storage device receives extensive research and application.Lithium ion battery is high with energy density, cycle life is good, work Make the advantages that voltage is high, security performance is high, environmentally protective and energy saving, in mobile phone, laptop and electric vehicle etc. Field plays an important role.Meanwhile the high speed development in these fields also proposes challenge to the energy density of lithium ion battery.
For current commercialized lithium battery due to the limitation of material system, energy density can be only sustained at 200~250Wh/ Kg is gradually unable to the growing demand of meet demand people.
Compared with lithium ion battery, lithium-sulfur cell has bigger energy density (2600Wh/kg) and bulk density (2800Wh/L).The theoretical capacity of sulphur simple substance has reached 1675mAh/g, and has cheap and advantages of environment protection, Therefore there are great potentiality in electrochemical energy storage field, receive people and widely study.But sulphur positive electrode is also deposited simultaneously In some impassable defects: the electronic conductivity of elemental sulfur is extremely low in room temperature, is the insulator of electronics and ion; Lithium-sulfur cell is soluble in the polysulfide of electrolyte easily generating in operation, generates " shuttle effect ", results in capacity Loss;The stable circulation performance that volume change in charge and discharge process also results in lithium-sulfur cell is bad, greatly hinders it The road of industrialization.
In view of the above problems, researcher usually carries out the modification of lithium sulphur battery electrode using following some strategies come excellent Change its electrochemical energy storage performance: sulphur simple substance and other high conductivity materials is compound, such as carbon material and metal material, it can be effective Increase its electric conductivity;Predetermined substance is added in sulphur simple substance, can effectively inhibit the dissolution and shuttle of polysulfide;In addition, The reasonable nano array structure of design construction, Lai Zeng great response area accelerate ionic conduction efficiency.Wherein, the first and carbon materials Expect that compound strategy has become one kind and generally acknowledges effective method of modifying.But the carbon material obtained is difficult to such as some comparisons Graphene, for mesoporous carbon, no matter from process flow or cost for all compare and be difficult to industrialization.Therefore, it invents A kind of cheap, with good conductivity carbon material is very urgent, while being also the first choice of building high-performance lithium-sulfur cell Scheme.
Summary of the invention
It is an object of the invention to be directed to soluble poorly conductive, the electrode of lithium-sulfur cell and volume change, mention A kind of sulphur-biomass carbon/transition metal combination electrode material and preparation method thereof is supplied, the composite material is with highly conductive Property, inhibit the advantages such as the gentle solution volume expansion of polysulfide dissolution.
The preparation method of sulphur-biomass carbon/transition metal combination electrode material of the present invention, comprising the following steps:
(1) rice is added in air flow puffing machine, seals and heats, heating temperature is 300~600 DEG C, and heated pressure is 0.5~1.2MPa, heating time are 1~5 minute, and puffed rice is obtained after pressure release;
(2) puffed rice is immersed in transition metal nitrate ethanol solution, takes out, obtains after impregnating 10~30 minutes The puffed rice of transition metal nitrate absorption;
(3) puffed rice that transition metal nitrate adsorbs is dried to obtain light green color transition metal nitrate absorption extruding Rice;
(4) light green color transition metal nitrate absorption puffed rice is subjected to high-temperature heat treatment in argon gas, at high warm Managing temperature is 700~1200 DEG C, and the high-temperature heat treatment time is 2~3 hours, obtains biomass carbon/transition metal composite material;
(5) biomass carbon/transition metal composite material is uniformly mixed with sulphur simple substance, is then placed in autoclave, 120~180 DEG C are heated to, heating time is 12~18 hours, after reaction kettle cooling, takes out reaction product, obtains sulphur-biology Matter carbon/transition metal combination electrode material.
It is used as the preferred technical solution of the present invention below:
In step (2), the transition metal nitrate ethanol solution is mixed by transition metal nitrate and ethyl alcohol.
The mass ratio of the puffed rice and transition metal nitrate is 3~4:1.
The ratio between quality and the volume of ethyl alcohol of the transition metal nitrate are 1g~5g:100mL, further preferably 3g:100mL.
The transition metal nitrate is one kind of nickel nitrate, cobalt nitrate, ferric nitrate, manganese nitrate, nitric acid tin, copper nitrate Or two or more (including two kinds).
The soaking temperature is 10~40 DEG C.
In step (3), the condition of the drying are as follows: be placed in 60~80 DEG C of dryings 20~40 minutes.
In step (5), the mass ratio of the biomass carbon/transition metal composite material and sulphur simple substance is 1:0.5~4, It further preferably, is 1:1.
Sulphur-biomass carbon/transition metal combination electrode material prepared by the present invention is answered by sulphur, biomass carbon and transition metal It closes, the transition metal is embedded in inside biomass carbon in a manner of metallic particles, wherein elemental sulfur weight percentage It is 10%~80%, carbon weight percentage composition is 18%~85%, and transition metal weight percentage composition is 2%~5%.
The transition metal is one or both of nickel, cobalt, iron, manganese, tin, copper, and the grain diameter of transition metal is 20~100nm.
Sulphur-biomass carbon/transition metal combination electrode material of the present invention has height ratio capacity, high rate capability and high circulation Service life, sun of the sulphur-biomass carbon/transition metal combination electrode material prepared by the present invention particularly suitable for preparing lithium-sulfur cell Pole.
Compared with prior art, the present invention has the advantage that
Sulphur-biomass carbon/transition metal the combination electrode material, the biomass carbon is after general rice extruding Obtained by high temperature cabonization;The transition metal is nickel, cobalt, iron, manganese, tin, the one or more of copper, the transition metal particles Partial size is 20~100nm, and the metallic particles is embedded in inside biomass carbon;Sulphur-biomass carbon/the transition metal Combination electrode material sulphur simple substance content be 10%~80%, carbon content be 18%~85%, levels of transition metals be 2%~ 5%;According to actual needs, its changes of contents can be controlled by adjusting reaction density and material.
The present invention is using biomass carbon as simple substance sulfur-donor, and by impregnating, high-temperature heat treatment method prepares biomass carbon/transition Metallic composite, then sulphur-biomass carbon/transition metal combination electrode material is prepared by sulfurizing method.Preparation method letter Folk prescription is just, easily controllable.
Lithium-sulfur cell sulphur-biomass carbon/transition metal combination electrode material prepared by the present invention, carbon material have biggish Specific surface area can increase the load capacity of elemental sulfur, provide bigger more effectively active reaction area, meanwhile, it is electrochemical reaction Good ion and electrons spread channel are provided, the diffusion length of ion is shortened, while improving electronics and ionic conductivity. Transition metal can effectively inhibit the dissolution of polysulfide, improve its cyclical stability, thus realize with high-energy density, The new energy of excellent cycle and reliable and secure novel lithium sulphur battery electrode material.Sulphur-biomass carbon/transition metal of the present invention is compound Electrode material have height ratio capacity, high rate capability and high circulation service life, mobile communication, electric car, solar power generation and The fields such as aerospace have broad application prospects.
Detailed description of the invention
Fig. 1 is sulphur-substance carbon/transition metal combination electrode material scanning electron microscope (SEM) photograph obtained in embodiment 1;
Fig. 2 is sulphur-substance carbon/transition metal combination electrode material scanning electron microscope (SEM) photograph obtained in embodiment 1;
Fig. 3 is sulphur-substance carbon/transition metal combination electrode material transmission electron microscope picture obtained in embodiment 1.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail, but the present invention is not limited to this.
Embodiment 1
It weighs 10.8g rice to be placed in air flow puffing machine, seals and heat, heating temperature is 300 DEG C, and heated pressure is 0.5Mpa, heating time are 5 minutes, and 10.8g puffed rice is obtained after rapid pressure release.
It weighs 3.0g nickel nitrate to be dissolved in 100ml ethanol solution, stirring to form nickel nitrate ethanol solution to being completely dissolved.So Puffed rice is transferred in nickel nitrate ethanol solution afterwards, 25 DEG C of immersions are taken out after ten minutes, 30 points dry under the conditions of 60 DEG C Clock obtains the puffed rice of nickel nitrate absorption.
It weighs in the puffed rice merging argon gas of 4.2g nickel nitrate absorption and is calcined 3 hours under the conditions of 700 DEG C, naturally cooled to 25 DEG C of room temperature, obtain biomass carbon/transition metal composite material.
2.0g biomass carbon/transition metal composite material and 2.0g elemental sulfur are weighed respectively and is uniformly mixed, and are then placed in In autoclave, 120 DEG C are heated to, heating time is 18 hours, after reaction kettle is down to 25 DEG C of room temperature, takes out reaction and produces Object obtains sulphur-substance carbon/transition metal combination electrode material.
Embodiment 2
It weighs 20.1g general rice to be placed in air flow puffing machine, seals and heat, heating temperature is 450 DEG C, heated pressure For 0.8Mpa, heating time is 3 minutes.20.1g puffed rice is obtained after rapid pressure release.
It weighs 6.0g nickel nitrate to be dissolved in 200ml ethanol solution, stirring to form nickel nitrate ethanol solution to being completely dissolved.So Puffed rice is transferred in ethanol solution afterwards, 25 DEG C of immersions are taken out after twenty minutes, and dry, the extruding for obtaining nickel nitrate absorption is big Rice.
It weighs in the puffed rice merging argon gas of 8.4g nickel nitrate absorption and is calcined 2.5 hours under the conditions of 950 DEG C, natural cooling To 25 DEG C of room temperature, biomass carbon/transition metal composite material is obtained.
4.0g biomass carbon/transition metal composite material and 4.0g elemental sulfur are weighed respectively and is uniformly mixed, and are then placed in In autoclave, 150 DEG C are heated to, heating time is 15 hours, after reaction kettle is down to 25 DEG C of room temperature, takes out reaction and produces Object obtains sulphur-substance carbon/transition metal combination electrode material.
Embodiment 3
It weighs 40.6g general rice to be placed in air flow puffing machine, seals and heat, heating temperature is 600 DEG C, heated pressure For 1.2Mpa, heating time is 1 minute.40.6g puffed rice is obtained after rapid pressure release.
It weighs 12.0g nickel nitrate to be dissolved in 400ml ethanol solution, stirring to form nickel nitrate ethanol solution to being completely dissolved. Then puffed rice is transferred in ethanol solution, 25 DEG C impregnate 30 minutes after take out, it is dry, obtain the extruding of nickel nitrate absorption Rice.
It weighs in the puffed rice merging argon gas of 16.8g nickel nitrate absorption and is calcined 2 hours under the conditions of 1200 DEG C, natural cooling To 25 DEG C of room temperature, biomass carbon/transition metal composite material is obtained.
8.0g biomass carbon/transition metal composite material and 8.0g elemental sulfur are weighed respectively and is uniformly mixed, and are then placed in In autoclave, 180 DEG C are heated to, heating time is 12 hours, after reaction kettle is down to 25 DEG C of room temperature, takes out reaction and produces Object obtains sulphur-substance carbon/transition metal combination electrode material.
Performance test
Using sulphur made of above-described embodiment 1~3-substance carbon/transition metal combination electrode material as anode, lithium metal is made Cathode, in argon atmosphere glove box assemble CR2025 button cell, electrolyte be 1mol/L LiTFSI/DOL:DEM (1: 1 volume ratio, DOL:1,3~dioxolanes;DME: glycol dimethyl ether), diaphragm is 2400 type of Celgard.Charge-discharge test exists Room temperature carries out, and instrument is blue electric battery test system, and test voltage range is relative to Li/Li+1.7~2.8V, loop test Electric current is 0.2C, and Rate test currents are 0.2C~5C, measures lithium-sulfur cell sulphur-substance carbon/transition metal combination electrode material Reversible charging and discharging capacity, charge-discharge performance and high-rate characteristics.
The performance test results are as follows:
Lithium-sulfur cell sulphur-biomass carbon/transition metal combination electrode material of embodiment 1, embodiment 2 and embodiment 3 Specific capacitance of discharging under 0.1A/g current density is respectively 1100mAh/g, 1080mAh/g and 1130mAh/g, and after 500 circulations Specific discharge capacity conservation rate is up to 80% or more.As it can be seen that lithium-sulfur cell sulphur-biomass carbon/transition metal compound electric obtained above Pole material charge/discharge capacity is high, good cycling stability.
Lithium-sulfur cell sulphur-biomass carbon/transition metal combination electrode material of embodiment 1, embodiment 2 and embodiment 3 exists Specific capacitance of discharging under 5A/g current density is respectively 343mAh/g, 386mAh/g and 320mAh/g.As it can be seen that lithium sulphur obtained above Battery sulphur-biomass carbon/transition metal combination electrode material high rate capability is good.
This is because on the one hand the incorporation of transition metal element improves the electric conductivity of entire composite material, on the other hand draw Enter the hole configurations that transition metal is formed on carbon skeleton and be conducive to increase the contact area of electrode and electrolyte, and provides more Big effective active reaction area, while good ion and electrons spread channel are provided for electrochemical reaction, shorten ion Diffusion length, improve battery performance.Secondly, transition metal particles have certain inhibition to make the shuttle effect of lithium-sulfur cell With, therefore the cycle performance of battery is improved again.
Therefore, lithium-sulfur cell sulphur-biomass carbon/transition metal combination electrode material of the present invention has height ratio capacity and Gao Xun Ring service life, high rate capability have in fields such as small-sized movable electronic equipment, electric car, solar power generation and aerospaces Wide application prospect.

Claims (10)

1. a kind of preparation method of sulphur-biomass carbon/transition metal combination electrode material, which comprises the following steps:
(1) by rice be added air flow puffing machine in, seal and heat, heating temperature be 300~600 DEG C, heated pressure be 0.5~ 1.2MPa, heating time are 1~5 minute, and puffed rice is obtained after pressure release;
(2) puffed rice is immersed in transition metal nitrate ethanol solution, is taken out after impregnating 10~30 minutes, obtains transition The puffed rice of metal nitrate absorption;
(3) by transition metal nitrate adsorb puffed rice be dried to obtain light green color transition metal nitrate absorption extruding it is big Rice;
(4) light green color transition metal nitrate absorption puffed rice is subjected to high-temperature heat treatment, high-temperature heat treatment temperature in argon gas Degree is 700~1200 DEG C, and the high-temperature heat treatment time is 2~3 hours, obtains biomass carbon/transition metal composite material;
(5) biomass carbon/transition metal composite material is uniformly mixed with sulphur simple substance, is then placed in autoclave, heating To 120~180 DEG C, heating time is 12~18 hours, after reaction kettle cooling, takes out reaction product, obtains sulphur-biomass Carbon/transition metal combination electrode material.
2. the preparation method of sulphur-biomass carbon/transition metal combination electrode material according to claim 1, feature exist In in step (2), the transition metal nitrate ethanol solution is mixed by transition metal nitrate and ethyl alcohol.
3. the preparation method of sulphur-biomass carbon/transition metal combination electrode material according to claim 2, feature exist In in step (2), the mass ratio of the puffed rice and transition metal nitrate is 3~4:1.
4. the preparation method of sulphur-biomass carbon/transition metal combination electrode material according to claim 2, feature exist In in step (2), the ratio between quality and the volume of ethyl alcohol of the transition metal nitrate are 1g~5g:100mL.
5. the preparation method of sulphur-biomass carbon/transition metal combination electrode material according to claim 2, feature exist In in step (2), the transition metal nitrate is nickel nitrate, cobalt nitrate, ferric nitrate, manganese nitrate, nitric acid tin, copper nitrate One or more.
6. the preparation method of sulphur-biomass carbon/transition metal combination electrode material according to claim 1, feature exist In in step (5), the mass ratio of the biomass carbon/transition metal composite material and sulphur simple substance is 1:0.5~4.
7. sulphur-biomass carbon/transition metal combination electrode of described in any item preparation method preparations according to claim 1~6 Material.
8. sulphur-biomass carbon/transition metal combination electrode material according to claim 7, which is characterized in that by sulphur, life Substance carbon and transition metal are combined, and the transition metal is embedded in inside biomass carbon in a manner of metallic particles, wherein Elemental sulfur weight percentage is 10%~80%, and carbon weight percentage composition is 18%~85%, and transition metal weight percentage contains Amount is 2%~5%.
9. sulphur-biomass carbon/transition metal combination electrode material according to claim 8, which is characterized in that the mistake Crossing metal is one or both of nickel, cobalt, iron, manganese, tin, copper.
10. preparing lithium sulphur according to the described in any item sulphur-biomass carbon/transition metal combination electrode materials of claim 7~9 Application in the anode of battery.
CN201611205892.4A 2016-12-23 2016-12-23 A kind of sulphur-biomass carbon/transition metal combination electrode material and its preparation method and application CN106532012B (en)

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CN108832088B (en) * 2018-06-08 2020-12-08 浙江大学 Biomass carbon/sodium vanadium phosphate composite electrode material and preparation method and application thereof
CN108682856A (en) * 2018-06-08 2018-10-19 浙江大学 The vanadium phosphate sodium nanocomposite and its preparation method and application of cattail carbon load
CN109273676B (en) * 2018-08-16 2020-08-18 浙江大学 Sulfur-mould spore carbon sphere/phosphide composite material and preparation method and application thereof
CN109698336B (en) * 2018-12-20 2020-08-18 浙江大学 Wrinkled sulfur-rice carbon/titanium carbide composite material and preparation method and application thereof
CN109698337B (en) * 2018-12-24 2020-10-16 浙江大学 Sulfur-spore carbon/niobium carbide composite electrode material and preparation method and application thereof
CN109686953B (en) * 2018-12-27 2020-10-27 杭州电子科技大学 Lithium-sulfur battery composite positive electrode material and preparation method thereof
CN109817931B (en) * 2019-01-24 2020-11-24 山东理工大学 C@TiO2Preparation method of @ biomass carbon composite negative electrode material
CN110047659A (en) * 2019-03-28 2019-07-23 南京理工大学 A kind of preparation method of biomass-based flexible electrode material
CN110931752A (en) * 2019-12-09 2020-03-27 华南师范大学 Nitrogen-doped porous carbon loaded metal nickel lithium-sulfur battery positive electrode material and preparation method and application thereof

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CN103236560B (en) * 2013-04-16 2016-06-08 浙江大学 A kind of sulfur/carbon composite anode material of lithium-sulfur cell and its preparation method and application
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