CN104201356A - Carbon nanotube array-polypyrrole-sulfur composite material - Google Patents

Carbon nanotube array-polypyrrole-sulfur composite material Download PDF

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Publication number
CN104201356A
CN104201356A CN201410454920.0A CN201410454920A CN104201356A CN 104201356 A CN104201356 A CN 104201356A CN 201410454920 A CN201410454920 A CN 201410454920A CN 104201356 A CN104201356 A CN 104201356A
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sulphur
composite material
carbon
carbon nano
polypyrrole
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赵宇光
钟毓娟
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NANJING ZHONGCHU NEW ENERGY Co Ltd
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NANJING ZHONGCHU NEW ENERGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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
    • 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 discloses a carbon nanotube array-polypyrrole-sulfur composite material, a preparation method thereof, and application of the carbon nanotube array-polypyrrole-sulfur composite material in a secondary aluminum battery. According to the composite material, a carbon nanotube array vertically growing on the surface of a conductive substrate serves as a conductive framework and is uniformly loaded with active substances, namely elemental sulfur and polypyrrole. The composite material can be directly taken as a positive electrode without a conductive agent or a binding agent and has the advantages of simple preparation process, low cost and high energy density. The secondary aluminum battery with the composite material is high in capacity and good in cycling performance.

Description

A kind of carbon nano pipe array-polypyrrole-sulphur composite material
Technical field
The invention belongs to battery material scientific domain, relate to a kind of carbon nano pipe array-polypyrrole-sulphur composite material and preparation method thereof.The invention still further relates to a kind of this composite material that adopts is anodal secondary aluminium cell.
Background technology
The develop rapidly of the new energy technologies such as regenerative resource is grid-connected, electric automobile and intelligent grid is in the urgent need to developing the more energy storage system of high-energy-density.Secondary aluminium-sulfur battery, as emerging battery system, is to take metallic aluminium as negative pole, and sulphur or sulfur-based compound are anodal battery system, have the features such as aboundresources, pollution-free, cheap, energy density is high, use is safe.The theoretical volume specific capacity of aluminium is 8050mAh/cm 3, be 4 times of lithium, and chemical activity is stable, be desirable negative material, and the theoretical volume specific capacity of sulphur is 3467mAh/cm 3, be one of positive electrode that known energy density is the highest.Yet, the dissolving in organic electrolyte due to the nonconducting natural quality of elemental sulfur and electric discharge intermediate product, easily cause the utilance of active material low, electrode passivation, the capacity loss of battery, the problems such as cycle performance is poor, one of approach of solution is with to have carbon-based material and conducting polymer materials that confinement effect, adsorption effect and conductivity are high compound by sulfur-bearing active material.
Wherein, carbon nano-tube has the advantages such as good conductivity, draw ratio are large, between them, can be barricaded as natural conductive network by bridge, is conducive to electrical conductivity and ion diffusion, is widely used in secondary battery electrode material.But traditional carbon nano-tube is unordered reunion shape, mainly by the absorption sulfur loaded of carbon nano tube surface, sulfur content in composite material is low, skewness.While discharging and recharging, a large amount of sulphur can directly dissolve in electrolyte from the surface of carbon nano-tube, causes the loss of active material, and energy content of battery density is difficult to improve.But be subject to the restriction of carbon-based material loose structure and surface chemistry, a little less than the interaction very on sulphur and carbon matrix surface, cause sulphur skewness in carbon matrix, these materials still existence and stability is poor, sulfur content is low and practical application in the shortcoming such as processing characteristics is limited.Therefore, only depend on the confinement effect of material with carbon element hole and the loss by dissolution that adsorption effect is difficult to thoroughly suppress poly sulfide, cycle performance can't reach practical degree.
Polypyrrole has higher conductivity, high energy storage capacity, good stability, high electrochemical redox characteristic, and ion can freely transmit in film, is a kind of ideal electrode material.But charcoal base electrode cycle life is unstable relatively, in charge and discharge process, can there is expansion and the contraction of volume, easily from electrode, come off.
Summary of the invention
(1) goal of the invention
For the problems referred to above and deficiency, the invention provides a kind of carbon nano pipe array-polypyrrole-sulphur composite material, described composite material is classified conducting matrix grain with vertical-growth as at the carbon nano-pipe array on conductive substrates surface, as carrier composite sulfur and polypyrrole active material.
Carbon nano pipe array has huge specific area can provide more load byte, can greatly improve the load capacity of sulphur; And the three-dimensional conductive network passage forming due to space between its orderly pore structure and pipe is nanoscale, can make sulfur-bearing active material dispersed with nano shape, closely compound with conducting matrix grain, effectively improve the reactivity of sulphur, simultaneously, to being filled in the sulphur in space in nanotube and between pipe, the orderly hole of these nanoscales and the major diameter of network channel and nanotube can produce than more confinement effect and the suction-operated of " long-range " of common carbon-based material, can suppress dissolving of sulfur-bearing reduzate in electrolyte, thereby slow down the loss of sulphur.
The pattern of polypyrrole is shaggy near-spherical, first in the coated one deck polypyrrole layer in conducting matrix grain surface, can effectively improve the specific area of composite material, for sulphur provides more load space, be conducive to realize the raising of sulfur loaded content, also be conducive to suppress to shuttle back and forth effect, improve the chemical property of electrode material simultaneously.Also first composite sulfur in conducting matrix grain, then at the coated one deck polypyrrole in its surface, can further slow down the loss of sulphur, can effectively promote again the transmission of electronics, promote the utilance of active material.
In addition, using described composite material as positive pole, without adding conductive agent and binding agent, can significantly improve the specific capacity of electrode, the energy density of electrode is also higher.
The object of the present invention is to provide a kind of carbon nano pipe array-polypyrrole-sulphur composite material and preparation method thereof.
The present invention also aims to provide a kind of and take carbon nano pipe array-polypyrrole-sulphur composite material as anodal secondary aluminium cell.
(2) technical scheme
For realizing foregoing invention, provide following technical scheme.
A carbon sulphur composite material, comprising:
1) vertical-growth is in the carbon nano pipe array on conductive substrates surface;
2) active material, is characterized in that, described active material comprises polypyrrole and sulphur.
Described carbon sulphur composite material, is characterized in that, the caliber of described carbon nano-tube is 1 ~ 50nm, pipe range 1 ~ 2000nm, tube pitch 2 ~ 100nm.
Described carbon sulphur composite material, it is characterized in that, the conductive substrates of described carbon nano pipe array includes but not limited to the metals or nonmetal such as carbon fiber, graphite, vitrescence carbon, titanium, nickel, stainless steel, iron, copper, zinc, lead, manganese, cadmium, gold, silver, platinum, tantalum, tungsten, conductive plastics, conductive rubber or highly doped silicon.
Described carbon sulphur composite material, is characterized in that, described active material is nano-scale, is evenly distributed in conducting matrix grain surface and space.
Described carbon sulphur composite material, is characterized in that, in described carbon sulphur composite material, the mass percent of sulphur, polypyrrole, carbon nano pipe array is respectively 60 ~ 80%, 15 ~ 30%, 5 ~ 10%.
Described carbon sulphur combination electrode, is characterized in that, carbon nano pipe array and sulphur are compound to be coated by polypyrrole again; Or carbon nano pipe array and polypyrrole are compound to be coated by sulphur again.
The preparation method of described carbon sulphur composite material, is characterized in that, comprising:
1) prepare carbon nano pipe array: first adopt chemical vapour deposition technique (CVD) to prepare carbon nano pipe array;
2) carbon sulphur composite material:
A. carbon nano pipe array and sulphur are compound is coated by polypyrrole again: first by the carbon nano pipe array preparing and sulphur in mass ratio 1:5 ~ 1:20 put into tube furnace, under inert gas shielding, be heated to 155 ~ 300 ℃, form sulphur-carbon nano-tube array composite material, then adopt chemical oxidization method at the coated one deck polypyrrole in the surface of sulphur-carbon nano-tube array composite material, make composite material;
B. carbon nano pipe array and polypyrrole are compound is coated by sulphur again: first adopt electrochemical method at the coated one deck polypyrrole in carbon nano pipe array surface, then by itself and sulphur in mass ratio 1:5 ~ 1:20 put into tube furnace, under inert gas shielding, be heated to 155 ~ 300 ℃ of formation combination electrodes; Or be placed in molten sulfur under inert gas shielding, keeping 5 ~ 10h, it is dry that taking-up product is put into baking oven, forms composite material.
Wherein, in above-mentioned steps A, chemical oxidization method is specific as follows: after sulphur-carbon nano-tube array composite material and pyrrole monomer are mixed by certain mass ratio, be dissolved in absolute ethyl alcohol, under ice-water bath condition, stir, in the backward mixture of temperature stabilization, add dopant p-methyl benzenesulfonic acid and initator ferric trichloride, after reaction a period of time, take out and at room temperature to stir 12 ~ 24h, after filtration, washing, vacuum drying, obtains carbon nano pipe array-polypyrrole-sulphur composite material.
In above-mentioned steps B, electrochemical method is specific as follows: configuration finite concentration Klorvess Liquid, in this solution, add pyrrole monomer, by the acidity of hydrochloric acid conditioning solution to pH=3.0, carbon nano pipe array is placed in to this mixed solution and soaks 20min, then the carbon nano-pipe array of take is classified work electrode, saturated calomel electrode as reference electrode, platinum electrode are as to electrode, adopt cyclic voltammetry to prepare polypyrrole, finally take out product, through distilled water flushing, the dry polypyrrole-carbon nano-tube array composite material that makes.
A secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that:
(a) positive pole, is characterized in that, carbon sulphur composite material just very claimed in claim 1;
(b) containing aluminium negative pole;
(c) non-water is containing aluminium electrolyte.
Secondary aluminium cell described in scheme also comprises the barrier film between positive pole and negative pole.Suitable solid porous diaphragm material includes but not limited to: polyolefin is as polyethylene and polypropylene, glass fiber filter paper and ceramic material.
Described in scheme containing aluminium negative active core-shell material, include but not limited to: aluminum metal, for example aluminium foil and be deposited on the aluminium on base material; Aluminium alloy, comprises and contains at least one element of being selected from Li, Na, K, Ca, Fe, Co, Ni, Cu, Zn, Mn, Sn, Pb, Ma, Ga, In, Cr, Ge and the alloy of Al.
Non-water described in scheme is organic salt-aluminum halide system ionic liquid containing aluminium electrolyte, and wherein, the mol ratio of organic salt and aluminum halide is 1:1.1 ~ 3.0.
In organic salt-aluminum halide system described in scheme, the cation of organic salt comprises imidazol ion, pyridinium ion, pyrroles's ion, piperidines ion, morpholine ion, quaternary ammonium salt ion ， quaternary alkylphosphonium salt ion and tertiary sulfosalt ion; The anion of organic salt comprises Cl -, Br -, I -, PF 6 -, BF 4 -, CN -, SCN -, [N (CF 3sO 2) 2] -, [N (CN) 2] -plasma.
Organic salt-aluminum halide system described in scheme, is characterized in that, described aluminum halide is a kind of in aluminium chloride, aluminium bromide or silver iodide.
Described in scheme, the preparation method of secondary aluminium cell is as follows: using described composite material be cut into 40mm wide * the thick pole piece of 15mm length * 0.33mm is as positive pole, be wound into battery core with the thick barrier film of 0.16mm and the negative pole made as negative active core-shell material with aluminium flake and pack nickel plating box hat into, the electrolyte that reinjects, secondary aluminium cell is made in sealing.
(3) beneficial effect
The invention provides a kind of carbon nano pipe array-polypyrrole-sulphur composite material, this composite material is classified conducting matrix grain with vertical-growth as at the carbon nano-pipe array on conductive substrates surface, uniform load sulfur-bearing active material therebetween, described sulfur-bearing active material is elemental sulfur and Pt/Polypyrrole composite material.Adopt this composite material for the secondary aluminium cell of anodal preparation, have the following advantages:
1) have three-dimensional conductive network structure and good mechanical strength, carbon nano pipe array and polypyrrole have the function of conductive agent, binding agent and collector, and production process is simple, can significantly improve specific capacity and the energy density of electrode.
2) carbon nano pipe array has huge specific area, and more load byte can be provided, and can greatly improve the load capacity of sulphur; And the three-dimensional conductive network passage forming due to space between its orderly pore structure and pipe is nanoscale, can make sulfur-bearing active material dispersed with nano shape, closely compound with conducting matrix grain, effectively improve the reactivity of sulphur.
3) nano pore of three-dimensional conducting matrix grain has strong suction-operated to intermediate products such as little molecular sulfur compounds, can realize fixing positive electrode active materials sulphur.
4) polypyrrole can effectively suppress to the coated of sulphur the effect of shuttling back and forth, and can further realize fixing to sulphur, suppresses sulphur and runs off.
5) apply the secondary aluminium cell of this anodal preparation, battery capacity is large, good cycle, safety and environmental protection.
(4) embodiment
Below with reference to embodiment, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.The following examples have been described several execution mode of the present invention, and they are only illustrative, and nonrestrictive.
Embodiment 1
(1) prepare carbon nano pipe array: take conductive paper of carbon fiber as substrate, Fe (NO 3) 3for catalyst, be coated in advance carbon paper surface, take methane as carbon source, nitrogen is protection gas, adopts chemical vapour deposition technique (CVD) to prepare carbon nano pipe array.
(2) combination electrode preparation: elemental sulfur is heated to 155 ℃; under nitrogen protection, the carbon nano pipe array preparing is put into wherein; keep 10 hours; put into 40 ℃ of baking ovens dry; keep 24 hours; form sulphur-carbon nano-tube array composite material; then by above-mentioned composite material and pyrrole monomer in mass ratio 3:1 after mixing, be dissolved in absolute ethyl alcohol; under ice-water bath condition, stir; in the backward mixture of temperature stabilization, add dopant p-methyl benzenesulfonic acid and initator ferric trichloride, the mol ratio of p-methyl benzenesulfonic acid/pyrroles/ferric trichloride is 0.75:1:0.5.After reaction 3h, take out and at room temperature to stir 24h, after filtration, washing, vacuum drying, obtains combination electrode.
(3) secondary aluminium cell preparation: take above-mentioned combination electrode as anodal, be cut into 40mm wide * pole piece that 15mm length * 0.33mm is thick, be wound into battery core with the thick non-negative pole of knitting barrier film and making as negative active core-shell material with aluminium flake of glass fibre of 0.16mm and pack nickel plating box hat into, aluminium chloride-triethylamine hydrochloride ionic liquid that reinjects, AA type cylinder secondary aluminium cell is made in sealing.
During battery charging and discharging loop test, with 1C, charge to 2.5V, 0.1C electric discharge, discharge cut-off voltage is 1.2V.Battery open circuit voltage is 1.80V, and high discharge capacity is 568mAh, and after 50 charge and discharge cycles, discharge capacity is 380mAh.
Embodiment 2
Employing stainless steel is substrate, and Fe is catalyst, take ethene as carbon source, and hydrogen and nitrogen are carrier gas, adopts chemical vapour deposition technique (CVD) to prepare carbon nano pipe array.All the other preparation methods and test are with embodiment 1.
Recording battery open circuit voltage is 1.74V, and high discharge capacity is 566mAh, and after 50 charge and discharge cycles, discharge capacity is 372mAh.
Embodiment 3
The preparation of carbon nano pipe array is with embodiment 1.
The preparation of combination electrode: configuration 0.2mol/L Klorvess Liquid, to the pyrrole monomer that adds 0.1mol/L in this solution, by the acidity of hydrochloric acid conditioning solution to pH=3.0, carbon nano pipe array is placed in to this mixed solution and soaks 20min, then the carbon nano-pipe array of take is classified work electrode, saturated calomel electrode as reference electrode, platinum electrode are as to electrode, adopt cyclic voltammetry to prepare polypyrrole, electro-deposition voltage is 0.7V, reaction time 0.5h; Finally take out product; through distilled water flushing, the dry polypyrrole-carbon nano-tube array composite material that makes; then elemental sulfur is heated to 155 ℃; under nitrogen protection, the polypyrrole-carbon nano-tube array composite material preparing is put into wherein; keep 10 hours; put into 40 ℃ of baking ovens dry, keep 24 hours, form combination electrode.
Other are with embodiment 1, and recording battery open circuit voltage is 1.78V, and high discharge capacity is 573mAh, and after 50 charge and discharge cycles, discharge capacity is 375mAh.
Embodiment 4
First elemental sulfur is heated to molten state, then polypyrrole-carbon nano-tube array composite material prepared in embodiment 3 is placed in one, keep 10h, it is dry that taking-up product is put into baking oven, forms combination electrode.
Method of testing is with embodiment 1, and recording battery open circuit voltage is 1.81V, and high discharge capacity is 570mAh, and after 50 charge and discharge cycles, discharge capacity is 382mAh.
Although the present invention is described in detail with reference to embodiment, but those skilled in the art is to be understood that, in the situation that do not depart from the spirit and scope of the present invention described in appended claims and equivalent thereof, can make various modifications and replacement to it.

Claims (8)

1. a carbon sulphur composite material, comprising:
1) vertical-growth is in the carbon nano pipe array on conductive substrates surface;
2) active material, is characterized in that, described active material comprises polypyrrole and sulphur.
2. carbon sulphur composite material as claimed in claim 1, is characterized in that, the caliber of described carbon nano-tube is 1 ~ 50nm, pipe range 1 ~ 2000nm, tube pitch 2 ~ 100nm.
3. carbon sulphur composite material as claimed in claim 1, it is characterized in that, the conductive substrates of described carbon nano pipe array includes but not limited to the metals or nonmetal such as carbon fiber, graphite, vitrescence carbon, titanium, nickel, stainless steel, iron, copper, zinc, lead, manganese, cadmium, gold, silver, platinum, tantalum, tungsten, conductive plastics, conductive rubber or highly doped silicon.
4. carbon sulphur composite material as claimed in claim 1, is characterized in that, described active material is nano-scale, is evenly distributed in conducting matrix grain surface and space.
5. carbon sulphur composite material as claimed in claim 1, is characterized in that, in described carbon sulphur composite material, the mass percent of sulphur, polypyrrole, carbon nano pipe array is respectively 60 ~ 80%, 15 ~ 30%, 5 ~ 10%.
6. carbon sulphur combination electrode as claimed in claim 1, is characterized in that, carbon nano pipe array and sulphur are compound to be coated by polypyrrole again; Or carbon nano pipe array and polypyrrole are compound to be coated by sulphur again.
7. a preparation method for carbon sulphur composite material claimed in claim 1, is characterized in that, comprising:
1) prepare carbon nano pipe array: first adopt chemical vapour deposition technique (CVD) to prepare carbon nano pipe array;
2) carbon sulphur composite material:
A. carbon nano pipe array and sulphur are compound is coated by polypyrrole again: first by the carbon nano pipe array preparing and sulphur in mass ratio 1:5 ~ 1:20 put into tube furnace, under inert gas shielding, be heated to 155 ~ 300 ℃, form sulphur-carbon nano-tube array composite material; Then adopt chemical oxidization method at the coated one deck polypyrrole in the surface of sulphur-carbon nano-tube array composite material, make composite material;
B. carbon nano pipe array and polypyrrole are compound is coated by sulphur again: first adopt electrochemical method at the coated one deck polypyrrole in carbon nano pipe array surface, then by itself and sulphur in mass ratio 1:5 ~ 1:20 put into tube furnace, under inert gas shielding, be heated to 155 ~ 300 ℃ of formation combination electrodes; Or be placed in molten sulfur under inert gas shielding, keeping 5 ~ 10h, it is dry that taking-up product is put into baking oven, forms composite material.
8. a secondary aluminium cell, comprises positive pole, negative pole and electrolyte, it is characterized in that:
(a) positive pole, is characterized in that, carbon sulphur composite material just very claimed in claim 1;
(b) containing aluminium negative pole;
(c) non-water is containing aluminium electrolyte.
CN201410454920.0A 2014-09-09 2014-09-09 Carbon nanotube array-polypyrrole-sulfur composite material Pending CN104201356A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116885196A (en) * 2023-09-06 2023-10-13 潍坊科技学院 Polypyrrole@three-dimensional cavity carbon skeleton composite electrode material and preparation and application thereof

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CN101662021A (en) * 2009-09-24 2010-03-03 无锡欧力达新能源电力科技有限公司 Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials
CN102593433A (en) * 2012-02-27 2012-07-18 清华大学 Directional carbon nano-tube composite cathode material for lithium-sulfur secondary battery
CN204257755U (en) * 2014-09-09 2015-04-08 南京中储新能源有限公司 A kind of carbon sulphur combination electrode and secondary aluminium cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101662021A (en) * 2009-09-24 2010-03-03 无锡欧力达新能源电力科技有限公司 Preparation methods of nano-coated positive electrode materials and secondary aluminium cell using nano-coated positive electrode materials
CN102593433A (en) * 2012-02-27 2012-07-18 清华大学 Directional carbon nano-tube composite cathode material for lithium-sulfur secondary battery
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116885196A (en) * 2023-09-06 2023-10-13 潍坊科技学院 Polypyrrole@three-dimensional cavity carbon skeleton composite electrode material and preparation and application thereof
CN116885196B (en) * 2023-09-06 2023-12-22 潍坊科技学院 Polypyrrole@three-dimensional cavity carbon skeleton composite electrode material and preparation and application thereof

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Application publication date: 20141210