CN109119626A - A kind of self-supporting lithium sulfur battery anode material carbon base body and preparation method - Google Patents

A kind of self-supporting lithium sulfur battery anode material carbon base body and preparation method Download PDF

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Publication number
CN109119626A
CN109119626A CN201810933292.2A CN201810933292A CN109119626A CN 109119626 A CN109119626 A CN 109119626A CN 201810933292 A CN201810933292 A CN 201810933292A CN 109119626 A CN109119626 A CN 109119626A
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base body
carbon
self
carbon base
anode material
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陈庆
廖健淞
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Chengdu New Keli Chemical Science 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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 present invention proposes a kind of self-supporting lithium sulfur battery anode material carbon base body and preparation method, the positive electrode carbon base body is containing addition carbon nanotube colloidal solution in chain organic matter/copper colloid particle solution system, form copper oxide/carbon nano-tube compound film material, add in trimesic acid solution impregnate reaction, last vacuum heating treatment, pickling and be made.Carbon base body provided by the invention has excellent stability and toughness, there are preferable absorption and dispersibility for element sulphur, the dispersion and expansion issues of the sulphur in traditional carbon base body can effectively be solved, the carrier mobility that anode can be improved simultaneously, can effectively facilitate the electric property and cyclical stability of lithium-sulfur cell.

Description

A kind of self-supporting lithium sulfur battery anode material carbon base body and preparation method
Technical field
The present invention relates to lithium-sulfur cell technical fields, more particularly to a kind of self-supporting lithium sulfur battery anode material carbon base body And preparation method.
Background technique
Lithium-sulfur cell is as a kind of very promising high-energy chemistry power supply, with electric car and portable electronic device Development, show higher theoretical specific capacity and theoretical specific energy, therefore widely paid close attention to by people.In addition, elemental sulfur Storage capacity is abundant, cheap, environmental-friendly, is most potential battery system in current high energy density cells field One of.
However, lithium-sulfur cell equally has many problems: (1) sulphur and sulfide electronic conductance and ionic conductivity are lower, It is unfavorable for the big multiplying power discharging of battery；(2) sulphur anode is larger in volume change rear in conjunction with lithium, and the 80% of reachable total volume, for It is larger with the compound influence of collection ear and collector；(3) interphase of more lithium sulfides such as Li2S6、Li2S8Deng dissolving in the electrolytic solution Spend it is larger, can shuttle with electrolyte to cathode of lithium side, cause the irreversible loss of sulphur anode, influence discharging efficiency and use the longevity Life.
To solve above-mentioned these problems, in recent years, mainly by studying and preparing composite positive pole, main at present point Sulphur/conducting polymer composite material, sulphur/metal oxide composite, vulcanize lithium electrode material for four classes: sulphur/carbon composite Material.Wherein, using conductive carbon material as the carrier of sulphur and the sulphur carbon composite anode material of conducting matrix grain, by regulating and controlling carbon material Structure prepare the composite material with different structure to improve the active material utilization and cycle performance of lithium-sulfur cell, at For research hotspot in recent years.
Chinese invention patent application number 201410748849.7 discloses a kind of lithium-sulfur cell porous carbon membranes and its in lithium Application in sulphur battery, with the mixture of organic polymer resin, organic polymer resin and inorganic nano-particle, organic high score The mixture of the mixture or organic polymer resin of subtree rouge and organic coordination compound and powder carbon material is raw material, preparation and At organic film or organic-inorganic composite membrane, by pre-oxidation, temperature programming carbonization, etching template, obtained porous carbon membranes.In Carbon fiber/sulphur that state application number of invention patent 201310426664.X discloses a kind of surface modification cellular carbon structure is compound just Pole material and preparation method thereof, the composite positive pole by surface modification cellular carbon structure carbon fiber and elemental sulfur it is compound and It is to first pass through solvent-thermal method to prepare metal organic frame cladding carbon fiber composite at, preparation method, then after high temperature carbonization, and Sulphur is compound to be obtained；Preparation method is simple, and the raw material of use is cheap.
In order to improve lithium-sulfur cell carbon sulphur positive electrode preparation process, improve dispersibility of the sulphur in carbon, effectively control The expansion of overall volume caused by sulphur atom processed, it is necessary to propose a kind of novel lithium sulfur battery anode material carbon base body, and then improve The cyclical stability of lithium-sulfur cell.
Summary of the invention
The shortcomings that there are carbon-sulphur to be unevenly distributed for existing lithium sulfur battery anode material, is difficult to control volume expansion, this Invention proposes a kind of self-supporting lithium sulfur battery anode material carbon base body and preparation method, to improve point of the sulphur in carbon base body Property is dissipated, and stability is good, is not easy to expand, circulating battery stability obtained is good.
To solve the above problems, the invention adopts the following technical scheme:
A kind of self-supporting lithium sulfur battery anode material carbon base body, the positive electrode carbon base body are to contain chain organic matter/copper Carbon nanotube colloidal solution is added in the solution system of colloidal solid, forms copper oxide/carbon nano-tube compound film material, adds In benzenetricarboxylic acid solution impregnate reaction, last vacuum heating treatment, pickling and be made.
Preferably, the chain organic matter is ethylaminoethanol, and the replacement of chain macromolecule can be used, and such as polyvinyl alcohol gathers The combination of one or more of amide, polyimides, polyurethane.
Preferably, the concentration of the trimesic acid solution is 2-5%, other can be used in the trimesic acid can carbon The aromatic series for turning to agraphitic carbon replaces.
The present invention also provides a kind of preparation method of self-supporting lithium sulfur battery anode material carbon base body, specific preparation methods It is as follows:
(1) copper nitrate is dissolved in mass concentration is to add complexing agent, still aging 6- in 20-40% chain organic solution After 10h, obtain containing chain organic matter/copper colloid particle solution system；
(2) the carbon nanotube colloidal solution that mass concentration is the surface 10-30% oxygen activation is added into solution system, is uniformly mixed Suspension is formed, is placed in electrostatic field, the two mutually absorption is made by statcoulomb power, is used after still aging 14-18h organic Membrane filtration, then the colloidal solid that filtering is obtained, in organic film surface levelling, low-temperature setting simultaneously removes organic matter, is aoxidized Copper/carbon nano-tube compound film material；
(3) copper oxide/carbon nano-tube film is added in trimesic acid solution and is impregnated, sufficiently taken out drying after reaction, obtain Benzenetricarboxylic acid copper/carbon nano-tube compound film；
(4) composite membrane is placed in vacuum drying oven, being divided into two stages is handled, and the first stage handles 3- at 150-160 DEG C 3.5h removes the crystallization water inside membrane material, and second stage handles 3-3.5h at 900-910 DEG C, and trimesic acid copper is made to be carbonized Porous agraphitic carbon is formed, is finally washed repeatedly using dilute nitric acid solution, is removed the metallic copper of precipitation, obtain porous agraphitic carbon It is piled into perforated membrane, and is connected with each other agraphitic carbon particle by carbon nanotube, as self-supporting lithium sulfur battery anode material Carbon base body.
Preferably, copper nitrate described in step (1) can be replaced with other transition metal, can be ferric nitrate, zinc nitrate, nitre The combination of one or more of sour manganese, nickel nitrate, cobalt nitrate, silver nitrate.
Preferably, complexing agent described in step (1) is sodium ammonium triacetate, disodium ethylene diamine tetraacetate, diethylenetriamine five The combination of one or more of five sodium of carboxylic acid, ethylenediamine tetraacetic methene sodium phosphate.
Preferably, in solution system described in step (1), chain organic solution, copper nitrate, complexing agent mass ratio For 100:30-50:3-6.
Preferably, organic film described in step (2) be teflon membrane filter, polyethersulfone membranes, the fine filter membrane of polypropylene, One of polystyrene filter membrane.
Preferably, in suspension described in step (2), solution system, carbon nanotube colloidal solution mass ratio be 100:50-80。
Preferably, the mass concentration of dilute nitric acid solution described in step (4) is 8-15%, and washing times are 6-10 times.
The sulphur carbon positive electrode of existing lithium-sulfur cell, there are sulphur content to dissipate unevenness, and volume expansion easily occurs for positive electrode Defect limits its application.In consideration of it, the present invention proposes a kind of self-supporting lithium sulfur battery anode material carbon base body and preparation side Copper nitrate is dissolved in aminoethanol solution by method, after addition complexing agent/flocculant is still aging, obtains chain organic matter/copper Colloidal solid, backward solution system in be added surface oxygen activation carbon nanotube colloidal solution, formed suspension, pass through electrostatic Coulomb force makes the two mutually absorption, is filtered after sufficient standing ageing using organic film, and the colloidal solid for filtering acquisition is being had Low-temperature setting and organic matter is removed after machine film surface levelling, obtains copper oxide/carbon nano-tube compound film material, be subsequently added into equal benzene three Impregnated in formic acid solution, sufficiently obtain trimesic acid copper/carbon nano-tube compound film after reaction, be placed in vacuum drying oven and carry out It handles twice, after the former removes the crystallization water inside membrane material, the latter makes trimesic acid copper be carbonized to form porous agraphitic carbon, most It is washed repeatedly using dilute nitric acid solution afterwards, removes the metallic copper of precipitation, obtain required self-supporting lithium sulfur battery anode material carbon Matrix.Carbon base body provided by the invention has excellent stability and toughness, has preferable absorption and dispersion energy for element sulphur Power, can effectively solve the dispersion and expansion issues of the sulphur in traditional carbon base body, while the carrier mobility of anode can be improved Rate can effectively facilitate the electric property and cyclical stability of lithium-sulfur cell.
The present invention proposes a kind of self-supporting lithium sulfur battery anode material carbon base body and preparation method, compared with prior art, Its feature protruded and excellent effect are:
1, load matrix of the laminated film prepared by the present invention as sulphur, has excellent stability and toughness, for sulphur member It is known as preferable absorption and dispersibility, can effectively solve the dispersion and expansion issues of the sulphur in traditional carbon base body.
2, carbon base body prepared by the present invention is interconnected to form three-dimensional by carbon nanotube between porous agraphitic carbon particle and leads Electric network further increases the carrier mobility of anode.
3, carbon base body produced by the present invention can effectively facilitate the electric property and cyclical stability of lithium-sulfur cell, before Jing Hao.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) copper nitrate is dissolved in mass concentration is to add complexing agent in 27% chain organic solution, after still aging 9h, It obtains containing chain organic matter/copper colloid particle solution system；Chain organic matter is ethylaminoethanol；Copper nitrate can use nitric acid Iron replaces；Complexing agent is sodium ammonium triacetate；In solution system, chain organic solution, copper nitrate, complexing agent mass ratio be 100:39:5；
(2) the carbon nanotube colloidal solution that mass concentration is 22% surface oxygen activation is added into solution system, is uniformly mixed and is formed Suspension is placed in electrostatic field, is made the two mutually absorption by statcoulomb power, is used organic film mistake after still aging 17h Filter, then the colloidal solid that filtering is obtained, in organic film surface levelling, low-temperature setting simultaneously removes organic matter, obtains copper oxide/carbon Nanometer tube composite film material；Organic film is teflon membrane filter；In suspension, solution system, carbon nanotube colloidal solution Mass ratio is 100:70；
(3) copper oxide/carbon nano-tube film is added in trimesic acid solution and is impregnated, sufficiently taken out drying after reaction, obtain Benzenetricarboxylic acid copper/carbon nano-tube compound film；The concentration of trimesic acid solution is 3%；
(4) composite membrane is placed in vacuum drying oven, being divided into two stages is handled, and the first stage handles 3h at 156 DEG C, is removed The crystallization water inside membrane material, second stage handle 3h at 903 DEG C, are finally washed repeatedly using dilute nitric acid solution to get propping up certainly Support lithium sulfur battery anode material carbon base body；The mass concentration of dilute nitric acid solution is 11%, and washing times are 9 times.
Test method:
The positive electrode carbon base body that the present embodiment prepares is tested for the property, after positive electrode carbon base body and sulphur review The positive plate that diameter is 14mm is made, metal lithium sheet is to pole, and diaphragm is Celgrad 2300, in the gloves of argon atmosphere In case MBRAUN LABSTAR Glove Box, by positive plate, electrolyte, diaphragm, lithium piece, gasket, shell assembled in sequence lithium Sulphur button half-cell, complete assembling battery place for 24 hours, at room temperature using new prestige cell tester to battery under 1C multiplying power into Row constant current charge-discharge test, voltage range 1.6-2.8V；Obtain the specific capacity of first charge-discharge first from test process, and The initial volume V of sulphur carbon positive electrode0, specific capacity and volume V when then testing charge and discharge cycles 200 times, 500 times respectivelyi, Positive plate surface sulphur content cloth situation of change is observed, cubical expansivity A=(V is calculatedi-V0)/V0× 100%, obtain result such as 1 institute of table Show.
Comparative example 1
Comparative example 1 compared with Example 1, is not used trimesic acid solution and impregnates membrane material, positive electrode carbon base body obtained is adopted It is tested with the method for embodiment 1, test result is as shown in table 1.
Embodiment 2
(1) copper nitrate is dissolved in mass concentration is to add complexing agent in 20% chain organic solution, after still aging 6h, It obtains containing chain organic matter/copper colloid particle solution system；Chain organic matter is polyvinyl alcohol；Copper nitrate can use nitric acid Zinc replaces；Complexing agent is disodium ethylene diamine tetraacetate；In solution system, the quality of chain organic solution, copper nitrate, complexing agent Ratio is 100:30:3；
(2) the carbon nanotube colloidal solution that mass concentration is 10% surface oxygen activation is added into solution system, is uniformly mixed and is formed Suspension is placed in electrostatic field, is made the two mutually absorption by statcoulomb power, is used organic film mistake after still aging 14h Filter, then the colloidal solid that filtering is obtained, in organic film surface levelling, low-temperature setting simultaneously removes organic matter, obtains copper oxide/carbon Nanometer tube composite film material；Organic film is polyethersulfone membranes；In suspension, the quality of solution system, carbon nanotube colloidal solution Ratio is 100:50；
(3) copper oxide/carbon nano-tube film is added in trimesic acid solution and is impregnated, sufficiently taken out drying after reaction, obtain Benzenetricarboxylic acid copper/carbon nano-tube compound film；The concentration of trimesic acid solution is 2%；
(4) composite membrane is placed in vacuum drying oven, being divided into two stages is handled, and the first stage handles 3.5h at 150 DEG C, removes The crystallization water inside membrane material is removed, second stage handles 3h at 900 DEG C, is finally washed repeatedly using dilute nitric acid solution to get certainly Support lithium sulfur battery anode material carbon base body；The mass concentration of dilute nitric acid solution is 8%, and washing times are 6 times.
It is tested using the method for embodiment 1, test result is as shown in table 1.
Comparative example 2
Comparative example 2 compared with Example 2, is not added with chain organic matter, and positive electrode carbon base body obtained uses the side of embodiment 1 Method is tested, and test result is as shown in table 1.
Embodiment 3
(1) copper nitrate is dissolved in mass concentration is to add complexing agent, still aging 10h in 40% chain organic solution Afterwards, it obtains containing chain organic matter/copper colloid particle solution system；Chain organic matter is polyamide；Copper nitrate can use nitre Sour manganese replaces；Complexing agent is five sodium of diethylenetriamine pentacarboxylic acid；In solution system, chain organic solution, copper nitrate, complexing agent Mass ratio be 100:50:6；
(2) the carbon nanotube colloidal solution that mass concentration is 30% surface oxygen activation is added into solution system, is uniformly mixed and is formed Suspension is placed in electrostatic field, is made the two mutually absorption by statcoulomb power, is used organic film mistake after still aging 18h Filter, then the colloidal solid that filtering is obtained, in organic film surface levelling, low-temperature setting simultaneously removes organic matter, obtains copper oxide/carbon Nanometer tube composite film material；Organic film is the fine filter membrane of polypropylene；In suspension, the matter of solution system, carbon nanotube colloidal solution Amount ratio is 100:80；
(3) copper oxide/carbon nano-tube film is added in trimesic acid solution and is impregnated, sufficiently taken out drying after reaction, obtain Benzenetricarboxylic acid copper/carbon nano-tube compound film；The concentration of trimesic acid solution is 5%；
(4) composite membrane is placed in vacuum drying oven, being divided into two stages is handled, and the first stage handles 3h at 160 DEG C, is removed The crystallization water inside membrane material, second stage handle 3h at 910 DEG C, are finally washed repeatedly using dilute nitric acid solution to get propping up certainly Support lithium sulfur battery anode material carbon base body；The mass concentration of dilute nitric acid solution is 15%, and washing times are 10 times.
It is tested using the method for embodiment 1, test result is as shown in table 1.
Comparative example 3
Comparative example 3 compared with Example 3, is not handled in a vacuum furnace, convection drying, and positive electrode carbon base body obtained is adopted It is tested with the method for embodiment 1, test result is as shown in table 1.
Embodiment 4
(1) copper nitrate is dissolved in mass concentration is to add complexing agent in 30% chain organic solution, after still aging 8h, It obtains containing chain organic matter/copper colloid particle solution system；Chain organic matter is polyimides；Copper nitrate can use nitric acid Nickel replaces；Complexing agent is ethylenediamine tetraacetic methene sodium phosphate；In solution system, the matter of chain organic solution, copper nitrate, complexing agent Amount ratio is 100:40:4；
(2) the carbon nanotube colloidal solution that mass concentration is 20% surface oxygen activation is added into solution system, is uniformly mixed and is formed Suspension is placed in electrostatic field, is made the two mutually absorption by statcoulomb power, is used organic film mistake after still aging 16h Filter, then the colloidal solid that filtering is obtained, in organic film surface levelling, low-temperature setting simultaneously removes organic matter, obtains copper oxide/carbon Nanometer tube composite film material；Organic film is polystyrene filter membrane；In suspension, the matter of solution system, carbon nanotube colloidal solution Amount ratio is 100:60；
(3) copper oxide/carbon nano-tube film is added in trimesic acid solution and is impregnated, sufficiently taken out drying after reaction, obtain Benzenetricarboxylic acid copper/carbon nano-tube compound film；The concentration of trimesic acid solution is 4%；
(4) composite membrane is placed in vacuum drying oven, being divided into two stages is handled, and the first stage handles 3h at 155 DEG C, is removed The crystallization water inside membrane material, second stage handle 3h at 905 DEG C, are finally washed repeatedly using dilute nitric acid solution to get propping up certainly Support lithium sulfur battery anode material carbon base body；The mass concentration of dilute nitric acid solution is 11%, and washing times are 8 times.
It is tested using the method for embodiment 1, test result is as shown in table 1.
Comparative example 4
Copper oxide/carbon nano-tube compound film material compared with Example 4, is directly used as carbon base body, anode material obtained by comparative example 4 Material carbon base body is tested using the method for embodiment 1, and test result is as shown in table 1.
Table 1:

Claims (10)

1. a kind of self-supporting lithium sulfur battery anode material carbon base body, which is characterized in that the positive electrode carbon base body is to contain Carbon nanotube colloidal solution is added in chain organic matter/copper colloid particle solution system, it is compound to form copper oxide/carbon nanotube Membrane material, add in trimesic acid solution impregnate reaction, last vacuum heating treatment, pickling and be made.
2. a kind of self-supporting lithium sulfur battery anode material carbon base body according to claim 1, which is characterized in that the chain Organic matter is ethylaminoethanol, can be used the replacement of chain macromolecule, such as polyvinyl alcohol, polyamide, polyimides, in polyurethane A combination of one or more.
3. a kind of self-supporting lithium sulfur battery anode material carbon base body according to claim 1, which is characterized in that the equal benzene The concentration of front three acid solution is 2-5%, and the trimesic acid can be used other and can be carbonized as the aromatic series generation of agraphitic carbon It replaces.
4. a kind of preparation method of self-supporting lithium sulfur battery anode material carbon base body as described in any claim of claim 1-3, It is characterized in that, it is specific the preparation method is as follows:
(1) copper nitrate is dissolved in mass concentration is to add complexing agent, still aging 6- in 20-40% chain organic solution After 10h, obtain containing chain organic matter/copper colloid particle solution system；
(2) the carbon nanotube colloidal solution that mass concentration is the surface 10-30% oxygen activation is added into solution system, is uniformly mixed Suspension is formed, is placed in electrostatic field, the two mutually absorption is made by statcoulomb power, is used after still aging 14-18h organic Membrane filtration, then the colloidal solid that filtering is obtained, in organic film surface levelling, low-temperature setting simultaneously removes organic matter, is aoxidized Copper/carbon nano-tube compound film material；
(3) copper oxide/carbon nano-tube film is added in trimesic acid solution and is impregnated, sufficiently taken out drying after reaction, obtain Benzenetricarboxylic acid copper/carbon nano-tube compound film；
(4) composite membrane is placed in vacuum drying oven, being divided into two stages is handled, and the first stage handles 3- at 150-160 DEG C 3.5h removes the crystallization water inside membrane material, and second stage handles 3-3.5h at 900-910 DEG C, and trimesic acid copper is made to be carbonized Porous agraphitic carbon is formed, is finally washed repeatedly using dilute nitric acid solution, is removed the metallic copper of precipitation, obtain porous agraphitic carbon It is piled into perforated membrane, and is connected with each other agraphitic carbon particle by carbon nanotube, as self-supporting lithium sulfur battery anode material Carbon base body.
5. a kind of preparation method of self-supporting lithium sulfur battery anode material carbon base body according to claim 4, feature exist In, copper nitrate described in step (1) can be replaced with other transition metal, can for ferric nitrate, zinc nitrate, manganese nitrate, nickel nitrate, The combination of one or more of cobalt nitrate, silver nitrate.
6. a kind of preparation method of self-supporting lithium sulfur battery anode material carbon base body according to claim 4, feature exist In complexing agent described in step (1) is sodium ammonium triacetate, disodium ethylene diamine tetraacetate, five sodium of diethylenetriamine pentacarboxylic acid, second two The combination of one or more of four methene sodium phosphate of amine.
7. a kind of preparation method of self-supporting lithium sulfur battery anode material carbon base body according to claim 4, feature exist In, in solution system described in step (1), chain organic solution, copper nitrate, complexing agent mass ratio be 100:30-50: 3-6。
8. a kind of preparation method of self-supporting lithium sulfur battery anode material carbon base body according to claim 4, feature exist In organic film described in step (2) is teflon membrane filter, polyethersulfone membranes, the fine filter membrane of polypropylene, polystyrene filter membrane One of.
9. a kind of preparation method of self-supporting lithium sulfur battery anode material carbon base body according to claim 4, feature exist In, in suspension described in step (2), solution system, carbon nanotube colloidal solution mass ratio be 100:50-80.
10. a kind of preparation method of self-supporting lithium sulfur battery anode material carbon base body according to claim 4, feature exist In the mass concentration of dilute nitric acid solution described in step (4) is 8-15%, and washing times are 6-10 times.
CN201810933292.2A 2018-08-16 2018-08-16 A kind of self-supporting lithium sulfur battery anode material carbon base body and preparation method Withdrawn CN109119626A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111500285A (en) * 2020-06-04 2020-08-07 山东丰益泰和科技有限公司 Method for synthesizing fluorescent carbon quantum dots by using citric acid and ethylene diamine tetramethylene sodium phosphate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111500285A (en) * 2020-06-04 2020-08-07 山东丰益泰和科技有限公司 Method for synthesizing fluorescent carbon quantum dots by using citric acid and ethylene diamine tetramethylene sodium phosphate
CN111500285B (en) * 2020-06-04 2023-01-17 山东丰益泰和科技有限公司 Method for synthesizing fluorescent carbon quantum dots by using citric acid and sodium ethylene diamine tetramethylene phosphate

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