CN107887608A - A kind of chalina that is carbonized carries preparation method of the sulphur as lithium sulfur battery anode material - Google Patents
A kind of chalina that is carbonized carries preparation method of the sulphur as lithium sulfur battery anode material Download PDFInfo
- Publication number
- CN107887608A CN107887608A CN201711101352.6A CN201711101352A CN107887608A CN 107887608 A CN107887608 A CN 107887608A CN 201711101352 A CN201711101352 A CN 201711101352A CN 107887608 A CN107887608 A CN 107887608A
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- chalina
- sulphur
- lithium
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of lithium sulfur battery anode material, is combined by carbonization chalina and sulphur, and described carbonization chalina has certain degree of graphitization and good electric conductivity.The invention provides a kind of preparation method and application of above-mentioned lithium sulfur battery anode material.It with chalina is that raw material prepares porous carbon that the lithium sulfur battery anode material of the present invention, which is, as sulphur body is carried, raw material natural green, easily obtain, prepared porous carbon good conductivity, specific surface area is big, and volume is big, and porosity is high, more sulphur can be accommodated, the dissolving of polysulfide in the electrolytic solution can preferably be suppressed, improve the charge-discharge performance of lithium-sulfur cell, keep its stability.
Description
First, technical field
The invention belongs to electrode material field, more particularly to a kind of lithium sulfur battery anode material and preparation method thereof.
2nd, background technology
New energy was substituting the fossil energy of increasingly depleted with regenerative resource in the last few years, it has also become this life is worked as in solution
One of effective means of boundary's energy crisis and environmental problem.And secondary cell as in new energy field energy storage device it is important
Part, become the study hotspot of new energy.Lithium-sulfur rechargeable battery is lived using the material of elemental sulfur or sulfur-bearing as positive pole
Property material, wherein sulphur is wider in distributed in nature, while has environment-friendly and high theory more excellent than energy (2600Wh/kg) etc.
Point, it is considered to be secondary cell most with prospects.Biological material is a kind of sustainable green material, is carbonized and sulphur
It is compound, apply and received much concern in lithium-sulfur cell.
The positive pole sulphur of lithium-sulfur cell is the insulator of electronics and ion, and in charge and discharge cycles, the Volume Changes of sulphur
Greatly, polysulfide is formed with negative pole lithium, these polysulfides are soluble in electrolyte, are produced shuttle effect, positive pole is lived
Property material utilization rate reduce, the capacity attenuation of battery is serious.
The SLAC (SLAC) and Stamford that Stanford University associate professor Cui Yi in 2013 takes the lead are big
Researcher have devised a kind of novel lithium sulphur electricity with sulphur titanium dioxide (S-TiO2) positive electrode of yolk-shell structure
Pond, when 0.5C discharges, initial specific capacities 1030mAh/g, after more than 1000 circulations, coulombic efficiency 98.4%.This electricity
After 1000 circulations, the capacity attenuation of each cycle only has 0.033%, shows good long-life performance in pond.
3rd, the content of the invention
It is an object of the invention to use the chalina of carbonization in lithium sulfur battery anode material as sulphur body is carried, using more
Pore structure and big specific surface area, the quick adsorption of sulphur is realized, prevent Volume Changes in charge and discharge process, it is molten to suppress polysulfide
Go out, effectively improve the cycle performance of lithium-sulfur cell.
A kind of lithium sulfur battery anode material carbonization chalina/sulphur of the present invention, its preparation method comprise the following steps:
(1) a certain amount of chalina is handled to a period of time in alkali source;
(2) product is dried;
(3) product is passed through inert gas in tube furnace, with 2~5 DEG C/min heating rate, is heated to 500
~900 DEG C of 1~2h of constant temperature;
(4) the product acid solution is fallen the alkali cleaning of residual, then with deionized water wash products for several times until
In neutrality.The product is finally dried in vacuo, and it is standby to collect product;
(5) product is mixed with sulphur source, after grinding a period of time, is put into the reactor of polytetrafluoroethyllining lining
In, 155~160 DEG C of 10~12h of holding are heated to, the positive electrode of lithium-sulfur cell is made.
Further, the alkali source in the step is one or both of potassium hydroxide, sodium hydroxide;
Further, acid solution is the one or more in hydrochloric acid, sulfuric acid, nitric acid;
Further, sulphur source is the one or more in sublimed sulfur, sodium thiosulfate, vulcanized sodium.;
Further, liquid phase dispersion medium is one kind in deionized water, ethanol, hydrochloric acid, sulfuric acid, nitric acid in the step
It is or several;
Further, 1) step handles a certain amount of chalina a period of time in alkali source in the step;
Further, inert gas is passed through 3) by the product in tube furnace in the step, with 2~5 DEG C/min's
Heating rate, it is heated to 500~900 DEG C of 1~2h of constant temperature;
Further, 4) cleaned in the step to neutrality.
The present invention obtains the chalina that is carbonized with alkali activation and high temperature cabonization chalina, then is mixed to prepare lithium-sulfur cell with sulphur
Positive electrode, method is simple, effectively suppresses the dissolution of polysulfide, improves the cyclical stability of battery.
4th, illustrate
Fig. 1 is the X-ray diffraction of carbonization chalina, carbonization chalina/sulfur materials and elemental sulfur prepared by embodiment 1
(XRD) figure.
Fig. 2 is first charge-discharge figure of the carbonization chalina/sulfur materials of the preparation of embodiment 1 under 0.1C.
Fig. 3 is the charge-discharge magnification curve map of carbonization chalina/sulfur materials prepared by embodiment 1.
5th, embodiment
Invention, rather than limitation of the invention further are intended to illustrate by the following examples.
Embodiment 1:(1) by a certain amount of chalina in 8M KOH solutions a period of time;(2) by the product certain
At a temperature of be dried;(3) product is passed through nitrogen in tube furnace, with 2 DEG C/min heating rate, is heated to 900
DEG C constant temperature 1h;(4) product is washed off the KOH of residual with 1M HCl solutions, it is then straight for several times with distilled water wash products
To in neutrality.The product is finally dried in vacuo, and it is standby to collect product;(5) product is mixed with elemental sulfur, grinds one section
After time, it is put into the reactor of polytetrafluoroethyllining lining, is heated to 160 DEG C of holding 12h, the positive pole material of lithium-sulfur cell is made
Material.
Carbonization chalina/sulphur target material, Super P and the aqueous binders LA132 of preparation are pressed into the ratio of certain mass
Example (70: 20: 10) weighs, and is put into small beaker, adds appropriate distilled water, after ultrasonic disperse is uniform, then is stirred and mixed well with glass bar
Until it is agglomerating to reunite.The shape material of reunion is put to be rolled with glass bar on a glass and is pressed into film, then film is made with blunderbuss
Disk, and being closely compressed on powder compressing machine on aluminium foil, is put into vacuum drying oven to take out in 45 DEG C of dry 12h and produces positive pole
Piece.Using metal lithium sheet as negative pole, for microporous polypropylene membrane Celgard2400 as barrier film, electrolyte is 1mol/L two (trifluoros
Pyrovinic acid) imine lithium (LiTFSI)/1,3 one dioxolanes (DOL)+glycol dimethyl ether (DME) solution (DOL and DME volumes
Than 1: 1), CR2032 type button simulated batteries are assembled into the JMS-3X type glove boxes full of argon gas.The simulation that will be assembled
After battery stands 4-6h at room temperature, tested in 1.7-2.8V charging/discharging voltage scopes.Test result shows:Material exists
Discharge capacity first under 0.1C multiplying power is 1531.6mAh/g, the discharge performance shown, and in 2.1V and 2.3V voltages
Nearby there are two constant voltage discharge platforms.The first charge-discharge curve and high rate performance curve of material are respectively such as Fig. 2, Fig. 3 institute
Show.
Embodiment 2:(1) a certain amount of chalina is immersed in a period of time in 8M KOH solutions;(2) product is existed
It is dried under certain temperature;(3) product is passed through nitrogen in tube furnace, with 2 DEG C/min heating rate, heating
To 500 DEG C of constant temperature 1h;(4) product is washed off the KOH of residual with 1M HCl solutions, then with distilled water wash products number
It is secondary until in neutrality.The product is finally dried in vacuo, and it is standby to collect product;(5) product is mixed with elemental sulfur, ground
After a period of time, it is put into the reactor of polytetrafluoroethyllining lining, is heated to 160 DEG C of holding 12h, lithium-sulfur cell is being made just
Pole material.Battery number of assembling steps is the same as example 1.
Embodiment 3:(1) a certain amount of chalina is immersed in a period of time in 8M KOH solutions;(2) product is existed
It is dried under certain temperature;(3) product is passed through nitrogen in tube furnace, with 2 DEG C/min heating rate, heating
To 600 DEG C of constant temperature 1h;(4) product is washed off the KOH of residual with 1M HCl solutions, then with distilled water wash products number
It is secondary until in neutrality.The product is finally dried in vacuo, and it is standby to collect product;(5) product is mixed with elemental sulfur, ground
After a period of time, it is put into the reactor of polytetrafluoroethyllining lining, is heated to 160 DEG C of holding 12h, lithium-sulfur cell is being made just
Pole material.Battery number of assembling steps is the same as example 1.
Embodiment 4:(1) a certain amount of chalina is immersed in a period of time in 8M KOH solutions;(2) product is existed
It is dried under certain temperature;(3) product is passed through nitrogen in tube furnace, with 2 DEG C/min heating rate, heating
To 700 DEG C of constant temperature 1h;(4) product is washed off the KOH of residual with 1M HCl solutions, then with distilled water wash products number
It is secondary until in neutrality.The product is finally dried in vacuo, and it is standby to collect product;(5) product is mixed with elemental sulfur, ground
After a period of time, it is put into the reactor of polytetrafluoroethyllining lining, is heated to 160 DEG C of holding 12h, lithium-sulfur cell is being made just
Pole material.Battery number of assembling steps is the same as example 1.
Embodiment 5:(1) a certain amount of chalina is immersed in a period of time in 8M KOH solutions;(2) product is existed
It is dried under certain temperature;(3) product is passed through nitrogen in tube furnace, with 2 DEG C/min heating rate, heating
To 800 DEG C of constant temperature 1h;(4) product is washed off the KOH of residual with 1M HCl solutions, then with distilled water wash products number
It is secondary until in neutrality.The product is finally dried in vacuo, and it is standby to collect product;(5) product is mixed with elemental sulfur, ground
After a period of time, it is put into the reactor of polytetrafluoroethyllining lining, is heated to 160 DEG C of holding 12h, lithium-sulfur cell is being made just
Pole material.Battery number of assembling steps is the same as example 1.
Claims (6)
- Chalina // magister of sulfur 1. a kind of lithium sulfur battery anode material is carbonized, it is characterised in that comprise the following steps that:(1) a certain amount of chalina is handled to a period of time in alkali source;(2) product is dried;(3) product is passed through inert gas in tube furnace, with 2~5 DEG C/min heating rate, it is heated to 500~ 900 DEG C of 1~2h of constant temperature;(4) the product acid solution is fallen the alkali cleaning of residual, then with deionized water wash products for several times until in being in Property.The product is finally dried in vacuo, and it is standby to collect product;(5) product is mixed with sulphur source, after grinding a period of time, is put into the reactor of polytetrafluoroethyllining lining, adds Heat keeps 10~12h to 155~160 DEG C, and the positive electrode of lithium-sulfur cell is made.
- 2. the method as described in claim 1, it is characterised in that:Alkali source used in the present invention is potassium hydroxide, in sodium hydroxide One or two.Acid solution used in the present invention is hydrochloric acid, the one or more in sulfuric acid, nitric acid.Used in the present invention Sulphur source is the one or more in sublimed sulfur, sodium thiosulfate, vulcanized sodium.Liquid dispersant used in the present invention is deionization One or both of water, ethanol, hydrochloric acid, sulfuric acid, nitric acid.
- 3. preparation method according to claim 1, it is characterised in that:Described (1) step is by a certain amount of chalina in alkali A period of time is handled in source.
- 4. preparation method according to claim 1, it is characterised in that:Described (3) step by the product in tube furnace, Inert gas is passed through, with 2~5 DEG C/min heating rate, is heated to 500~900 DEG C of 1~2h of constant temperature.
- 5. preparation method according to claim 1, it is characterised in that:Described (4) step is by the product acid solution The alkali cleaning of residual is fallen, then with deionized water wash products for several times until in neutrality.
- 6. preparation method according to claim 1, it is characterised in that:The inert gas is nitrogen or argon gas.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109256553A (en) * | 2018-09-28 | 2019-01-22 | 桑顿新能源科技有限公司 | A kind of porous bamboo carbon carries sulphur composite positive pole, preparation method and lithium battery |
CN109473647A (en) * | 2018-11-01 | 2019-03-15 | 东莞市迈科新能源有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
CN110350176A (en) * | 2019-07-11 | 2019-10-18 | 安徽师范大学 | Egg white carbonization prepares micro-nano porous carbon sulfur loaded composite material, preparation method and applications |
CN111960401A (en) * | 2020-08-27 | 2020-11-20 | 江南大学 | Biomass-based phase-change latent heat energy storage material and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104098083A (en) * | 2014-07-15 | 2014-10-15 | 黑龙江大学 | Method for preparing porous nano carbon materials with biomass serving as carbon source |
CN104108713A (en) * | 2014-07-25 | 2014-10-22 | 哈尔滨工业大学深圳研究生院 | Preparation methods and application of porous carbon from towel gourd vegetable sponge and composite material of porous carbon |
CN104681800A (en) * | 2015-03-09 | 2015-06-03 | 安康学院 | Corn straw based biological carbon/sulfur composite material as well as preparation method and application thereof |
CN104900880A (en) * | 2015-06-03 | 2015-09-09 | 中国地质大学(武汉) | Lithium-sulfur battery composite positive electrode material and preparation method thereof |
CN106887566A (en) * | 2015-12-11 | 2017-06-23 | 中科派思储能技术有限公司 | A kind of method that agaric that is carbonized prepares carbon material or lithium sulfur battery anode material |
-
2017
- 2017-11-09 CN CN201711101352.6A patent/CN107887608A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104098083A (en) * | 2014-07-15 | 2014-10-15 | 黑龙江大学 | Method for preparing porous nano carbon materials with biomass serving as carbon source |
CN104108713A (en) * | 2014-07-25 | 2014-10-22 | 哈尔滨工业大学深圳研究生院 | Preparation methods and application of porous carbon from towel gourd vegetable sponge and composite material of porous carbon |
CN104681800A (en) * | 2015-03-09 | 2015-06-03 | 安康学院 | Corn straw based biological carbon/sulfur composite material as well as preparation method and application thereof |
CN104900880A (en) * | 2015-06-03 | 2015-09-09 | 中国地质大学(武汉) | Lithium-sulfur battery composite positive electrode material and preparation method thereof |
CN106887566A (en) * | 2015-12-11 | 2017-06-23 | 中科派思储能技术有限公司 | A kind of method that agaric that is carbonized prepares carbon material or lithium sulfur battery anode material |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109256553A (en) * | 2018-09-28 | 2019-01-22 | 桑顿新能源科技有限公司 | A kind of porous bamboo carbon carries sulphur composite positive pole, preparation method and lithium battery |
CN109473647A (en) * | 2018-11-01 | 2019-03-15 | 东莞市迈科新能源有限公司 | A kind of lithium sulfur battery anode material and preparation method thereof |
CN110350176A (en) * | 2019-07-11 | 2019-10-18 | 安徽师范大学 | Egg white carbonization prepares micro-nano porous carbon sulfur loaded composite material, preparation method and applications |
CN111960401A (en) * | 2020-08-27 | 2020-11-20 | 江南大学 | Biomass-based phase-change latent heat energy storage material and preparation method thereof |
CN111960401B (en) * | 2020-08-27 | 2022-05-10 | 江南大学 | Biomass-based phase-change latent heat energy storage material and preparation method thereof |
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Application publication date: 20180406 |