CN109346691A - A kind of preparation method of lithium sulfur battery anode material - Google Patents
A kind of preparation method of lithium sulfur battery anode material Download PDFInfo
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- CN109346691A CN109346691A CN201811165866.2A CN201811165866A CN109346691A CN 109346691 A CN109346691 A CN 109346691A CN 201811165866 A CN201811165866 A CN 201811165866A CN 109346691 A CN109346691 A CN 109346691A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to a kind of preparation methods of lithium sulfur battery anode material, belong to battery material technical field.It is low and easily the phenomenon that volume expansion occur in order to solve existing loading, a kind of preparation method of lithium sulfur battery anode material is provided, this method includes that anionic surfactant is added in solvent to be configured to microemulsion, and acid reagent tune pH value is added in acid；Conducting polymer monomer and metal salt are added into microemulsion, then, oxidant are added and excessive metal powder is reacted, after, solid mixture is collected by filtration, washs, obtains corresponding conductive metal/conducting polymer composite material；High temperature sintering processing is carried out after conductive metal/conducting polymer composite material and elemental sulfur are mixed, obtains corresponding sulphur anode composite material.The present invention can be improved load capacity of the metal on cellular conducting polymer, improves the effect of its skeletal support and conductive capability, has high stability and cycle performance of battery.
Description
Technical field
The present invention relates to a kind of preparation methods of lithium sulfur battery anode material, belong to battery material technical field.
Background technique
Lithium-sulfur cell is a kind of lithium battery using element sulphur as anode, and elemental sulfur theoretical discharge specific capacity is reachable
To 1675mAh/g, significantly larger than commercial widely applied lithium ion battery.Therefore, sulphur positive active material is that have at present
The positive electrode of highest specific capacity, lithium are in metallic element with the smallest relative atomic mass and most negative normal electrode electricity
Gesture.Therefore, lithium-sulfur cell has high theoretical discharge voltage, high theoretical discharge specific capacity, high theoretical specific energy, is expected to meet electronic
The long term growth requirement of automobile, is a kind of very promising lithium battery.It is reported that the practical specific energy of lithium-sulfur cell has reached
350Wh kg-1.But stage lithium-sulfur cell faces a series of problems: 1. elemental sulfurs and discharging product Li now2S2/Li2S is electronics
With ion insulator, which increase cell resistance and polarization phenomena；2. there is volume expansions during discharge for positive electrode
Phenomenon causes material structure to collapse, and influences the cycle performance of battery；3. the soluble polysulfide generated in charge and discharge process,
Due to diffusion between positive and negative anodes transport reaction, occur " the shuttle effect " of polysulfide, cause active material irreversible
Loss.
In order to solve the problems, such as that lithium-sulfur cell faces, also has at present by largely studying, be concentrated mainly on following
Aspect: (1) conductive capability of electrode material is improved；(2) it is swollen to alleviate volume during lithiumation to design the structure of electrode material
It is swollen；(3) inhibit the dissolution etc. of polysulfide in the electrolytic solution.
The electrology characteristic of the existing metal of conducting polymer, and flexibility and machinability with organic polymer, also have
There are electrochemical redox activity and storage lithium performance.These features determine that conducting polymer is improving lithium-sulfur cell aspect of performance
It can play an important role.In sulphur/conducting polymer composite material, conducting polymer has dispersing agent, adsorbent, conductive addition
Agent and the effect for maintaining cathode material structure stable, make the utilization rate of sulphur and cycle performance obtain largely improving.Such as
Chinese patent application (publication No.: CN1396202A) proposes a kind of elemental sulfur/conducting polymer composite material and method, the party
Method is only simply compound with conducting polymer by elemental sulfur, cannot construct the structure and shape to form cavernous composite material
Looks, the phenomenon that loading cannot being avoided well low and volume expansion.
Summary of the invention
The present invention is directed to the above defect existing in the prior art, provides a kind of preparation side of lithium sulfur battery anode material
How the technical issues of method, solution improves loading and reduces volume expansion.
The purpose of the present invention is achieved by the following technical programs, a kind of preparation method of lithium sulfur battery anode material,
It is characterized in that, method includes the following steps:
A, anionic surfactant is added in solvent and is configured to microemulsion, acid reagent tune pH value is added in acid
Property；
B, conducting polymer monomer and metal salt are added into microemulsion above-mentioned, then, oxidant and excessive is added
Metal powder is reacted, after, solid mixture is collected by filtration, then acid solution is added into solid mixture and is washed till filtrate
It is in neutrality or faintly acid, after then being washed with water and/or alcohol, obtains corresponding conductive metal/conducting polymer composite material；
C, high temperature sintering processing is carried out after mixing conductive metal/conducting polymer composite material and elemental sulfur, obtains phase
The lithium sulfur battery anode material answered.
The present invention is by mixing one for metal salt and conducting polymer monomer and excessive metal powder in microemulsion
It rises and is reacted, make displacement reaction and the generation of conducting polymer reaction while carrying out, the conducting polymer prepared can be made
Not only with the nanosphere or porous nanotube structure of Porous hollow, meanwhile, it is capable to make to support on the surface of conducting polymer
Corresponding metallic conductor further increases the electrical conductive activities and mechanical strength of polymer；Finally, making simple substance by heat treatment again
Sulphur is supported on Porous hollow shape nanosphere and porous nanotube surfaces externally and internally, substantially increases the loading of sulphur, and effectively
Inhibit " shuttle effect " of the polysulfide in charge and discharge process, and it is swollen greatly to alleviate the volume during sulphur lithiumation
It is swollen, to effectively improve the cycle performance of battery.
In the preparation method of above-mentioned lithium sulfur battery anode material, preferably, metal powder described in step B is selected from aluminium
One or more of powder, magnesium powder, iron powder and copper powder.Displacement occurs with metal ion in metal salt by metal powder to react,
So that the metal in metal salt is effectively supported on conducting polymer, improves its skeletal support ability and have and preferably lead
Electrical property is also beneficial to form the conducting polymer structures characteristic of Porous hollow, improves the loading in its surfaces externally and internally.Here
To the progress reacted is replaced when selecting metal powder, preferably according to the characteristic of metal active, selection can be with gold in metal salt
Belong to the metal powder that displacement reaction occurs for ion to effectively improve metal in conducting polymer to guarantee effective progress of reaction and lead
Body.
In the preparation method of above-mentioned lithium sulfur battery anode material, preferably, metal salt described in step B is selected from nitric acid
One or more of copper, copper sulphate, copper chloride, silver nitrate and chlorauride.
In the preparation method of above-mentioned lithium sulfur battery anode material, preferably, acid solution hydrochloric acid described in step B,
It is one or more in nitric acid, sulfuric acid, hypochlorous acid, perchloric acid, formic acid, acetic acid, malonic acid, tartaric acid, benzoic acid and citric acid.It is logical
The washing of peracid solutions can effectively remove excessive metal powder.Here preferably make using mass fraction 5%~
70% acid solution (here not including hydrochloric acid solution), further can adopt nitric acid, sulfuric acid, hypochlorous acid or perchloric acid etc.
With the dilute solution of respective acids, improve the safety of operation, for hydrochloric acid solution can be mass fraction be 5%~
20%.
In the preparation method of above-mentioned lithium sulfur battery anode material, preferably, conducting polymer monomer described in step B
Molar ratio with metal salt is 20:1~1:2.It can promote the progress of polymerization reaction.It is further preferred, institute can also be made
The molar ratio for stating anionic surfactant and conducting polymer monomer is 1:10~5:1, oxidant and conducting polymer monomer
Molar ratio be 5:1~1:2.
In the preparation method of above-mentioned lithium sulfur battery anode material, preferably, conducting polymer monomer described in step B
It is one or more in 3,4-- ethene dioxythiophene, pyrroles, aniline, thiophene and acetylene.
In the preparation method of above-mentioned lithium sulfur battery anode material, preferably, oxidant described in step B is selected from over cure
In acid sodium solution, potassium persulfate solution, ammonium persulfate solution, ferric chloride solution, p-methyl benzenesulfonic acid ferrous solution and cerous sulfate solution
It is one or more.
It in the preparation method of above-mentioned lithium sulfur battery anode material, carry out reaction can effectively.Make
To be preferred, the temperature of reaction described in step B is -20~100 DEG C, preferably makes 0~10 DEG C of temperature of reaction.
In the preparation method of above-mentioned lithium sulfur battery anode material, preferably, the anionic surfactant is selected from
Carboxylate surfactant, sulfonate surfactant, sulfuric ester salt form surfactant and phosphate salt form surface are living
It is one or more in property agent.Allow to form micro- supernatant liquid, is conducive to the formation of the porous hollow of subsequent conductive polymer, mentions
The advantages of high load amount.As further preferably, the carboxylate surfactant is selected from higher fatty acid salt, three second
One or more of alcohol ammonium salt and N- oleoyl polypeptide；The sulfonate surfactant is selected from 2- sodium naphthalene sulfonate, 12
Sodium alkyl benzene sulfonate, dodecane sulfonate, N- oleoyl N-methyl sodium taurocholate and to methoxyl group fatty acyl anilinesulfonic acid
One or more of sodium；The sulfuric ester salt form surfactant in sulphation natrium ricinoleicum, cycloalkanes sodium sulphate one
Kind or two kinds, the phosphate salt form surfactant be selected from one of alkyl phosphate monoester salt and alkyl phosphoric acid dibasic acid esters salt or
Two kinds.Here 0.1~the 1.0M of concentration for preferably making microemulsion can also make when preparing microemulsion using mass concentration
The pH value of 5%~40% acid solution tune system is 1~7.Wherein, acid solution can be selected from hydrochloric acid, nitric acid, sulfuric acid, secondary
One or more of chloric acid, perchloric acid, formic acid, acetic acid, malonic acid, tartaric acid, benzoic acid and citric acid.Here micro emulsion is prepared
The solvent used when liquid can be deionized water, be also possible to the alcoholic solvent of low molecular weight such as ethyl alcohol, n-butanol, normal propyl alcohol, different
Propyl alcohol, n-amyl alcohol, carbitol etc. are also possible to ethylene glycol, propylene glycol etc.；Or can also be acetone, chloroform, benzene, toluene and
One or more of ether etc..Alcoholic solvent or deionized water are preferably used, not only raw material is easy to get, and toxicity is smaller, favorably
In safety in production.
In the preparation method of above-mentioned lithium sulfur battery anode material, preferably, the processing of high temperature sintering described in step C
Specifically: temperature is first controlled in 100~200 DEG C of constant temperature and handles 2~48h, then, then controls temperature at 200~400 DEG C of constant temperature
1~10h is managed, finally, cooled to room temperature, obtains sulphur anode composite material.It is supported on sulphur active material more effectively more
On poroid conducting polymer, obscission is avoided the occurrence of, inhibits Study of Volume Expansion of the polysulfide in charge and discharge process,
The volume expansion during sulphur lithiumation is greatly alleviated, to effectively improve the cycle performance of battery.
In conclusion compared with prior art, the present invention having the advantage that
1. being jointly added in reaction system by using excessive metal powder and metal salt, make displacement reaction and conduction
Polymer generates reaction while carrying out, and metallic conductor is supported in conducting polymer, the conduction of polymer is further increased
Property and mechanical strength, reduce the internal resistance of cell, improve in charge and discharge process material structure stability, allow to effectively form
The conducting polymer of porous hollow is conducive to the effect for improving loading.
2. can effectively make sulphur be supported in its surface or hole, effectively due to the formation of porous hollow characteristic
The load capacity for improving sulphur, effectively inhibits " shuttle effect " of the polysulfide in charge and discharge process, and greatly alleviate
Volume expansion during sulphur lithiumation, to effectively improve the cycle performance of battery.
Detailed description of the invention
Fig. 1 be the respective battery that the embodiment of the present invention obtains 0.5C under charge-discharge performance and coulombic efficiency analysis
Figure.
Specific embodiment
Below by specific embodiments and the drawings, the technical solutions of the present invention will be further described, but this
Invention is not limited to these examples.
Embodiment 1
It takes a certain amount of dodecyl sodium sulfate to be dissolved in deionized water, is uniformly mixed, make the micro emulsion to form 0.1M
Liquid system, then, adding mass fraction is the pH value of 10% hydrochloric acid regulation system to 4, makes system in acidity, spare.
The microemulsion that 50mL is above-mentioned is taken, then adds the aniline monomer of 0.02moL and 0.17g silver nitrate is stirred and ultrasound
It is uniformly dispersed, then, then oxidant ammonium persulfate solution is slowly added dropwise under stirring (makes mole of aniline and ammonium persulfate
It is controlled in entire reaction process than for 1:1) and being slowly added to excessive aluminium powder simultaneously wait be stirred for reaction 12h after dripping
The reaction temperature of system is 0~5 DEG C, and suction filtration obtains corresponding solid mixture, then quality is slowly added into solid mixture
The diluted nitric acid aqueous solution that concentration is 10%, which is washed to filtrate, to be in neutrality, and is finally centrifuged repeatedly and is washed with a large amount of deionized water, ethyl alcohol
It washs, obtains cavernous hollow conductive metal/conductive polymer nanometer pipe.
Cavernous hollow conductive metal/conductive polymer nanometer pipe obtained above and elemental sulfur is taken (to make the matter of the two
Amount is uniformly mixed it than carrying out grinding in mortar for 1:1) mixture, is subsequently placed in the reaction kettle full of argon gas or nitrogen
In, then reaction kettle is put into Muffle furnace, it is heated up with the speed that heating rate is 2 DEG C/min, and control perseverance of the temperature at 157 DEG C
Under the conditions of temperature after high temperature sintering processing 18h, then under 280 DEG C of constant temperature 4h is handled, finally, cooled to room temperature obtains
Lithium sulfur battery anode material.
Performance test after obtained material to be carried out to battery assembly, wherein battery assembly and test are as follows:
It chooses the above-mentioned sulphur anode composite material of 0.8g, 0.1g acetylene black and 0.1g Kynoar and is added to N- methylpyrrole
It is stirred dispersion in alkanone and obtains anode sizing agent, slurry coating is dried to obtain battery anode slice, and using lithium piece as cathode, uses
Celgard2400 diaphragm is added dropwise 25 μ l electrolyte, CR2032 button cell is assembled into glove box and is tested accordingly.
Specifically: make charge and discharge blanking voltage 1.7V~2.8V (vs.Li/Li+)。
Under 0.5C charge and discharge carry out cycle performance test, the composite material its show good cycle performance.Such as Fig. 1
Shown, which reaches 941mAh g-1, coulombic efficiency reaches 98%, by 100 circulation volumes
It is maintained at 508mAh g-1, coulombic efficiency reaches 78%.
Embodiment 2
It takes a certain amount of sulphation natrium ricinoleicum to be dissolved in deionized water, is uniformly mixed, make the micro emulsion to form 0.2M
Liquid system, then, adding mass percent is the pH value of 20% hydrochloric acid regulation system to 1, makes system in acidity, spare.
The microemulsion that 50mL is above-mentioned is taken, then adds the pyrrole monomer of 0.01moL and 0.08g silver nitrate is stirred and ultrasound
It is uniformly dispersed, then, then oxidant ferric chloride solution is slowly added dropwise under stirring (makes the molar ratio of pyrroles and iron chloride
It 1:1) and is simultaneously slowly added to excessive aluminium powder, wait be stirred for reaction 12h, control system in entire reaction process after dripping
Reaction temperature be 5~10 DEG C, suction filtration obtains corresponding solid mixture, then quality percentage is slowly added into solid mixture
Number is in neutrality for 15% dust technology to filtrate, is finally centrifuged repeatedly washing with a large amount of deionized water, ethyl alcohol, obtains cellular
Hollow conductive metal/conductive polymer nanometer pipe.
Cavernous hollow conductive metal/conductive polymer nanometer pipe obtained above and elemental sulfur is taken (to make the matter of the two
Amount is uniformly mixed it than carrying out grinding in mortar for 1:3) mixture, is subsequently placed in the reaction kettle full of argon gas or nitrogen
In, then reaction kettle is put into Muffle furnace, it is heated up with the speed that heating rate is 5 DEG C/min, and control perseverance of the temperature at 160 DEG C
Under the conditions of temperature after high temperature sintering processing 10h, then under 285 DEG C of constant temperature 2h is handled, finally, cooled to room temperature obtains
Lithium sulfur battery anode material.
Performance test after obtained material to be carried out to battery assembly, wherein battery assembly and test are as follows:
It chooses the above-mentioned sulphur anode composite material of 0.8g, 0.1g acetylene black and 0.1g Kynoar and is added to N- methylpyrrole
It is stirred dispersion in alkanone and obtains anode sizing agent, slurry coating is dried to obtain battery anode slice, and using lithium piece as cathode, uses
Celgard2400 diaphragm is added dropwise 25 μ l electrolyte, CR2032 button cell is assembled into glove box and is tested accordingly.
Specifically: make charge and discharge blanking voltage 1.7V~2.8V (vs.Li/Li+)。
Under 0.5C charge and discharge carry out cycle performance test, the composite material its show good cycle performance.This is multiple
The first discharge specific capacity of the respective battery of condensation material reaches 955mAh g-1, coulombic efficiency reaches 98.5%, follows by 100 times
Ring capacity is maintained at 524mAh g-1, coulombic efficiency reaches 80.2%.
Embodiment 3
It takes a certain amount of pair of methoxyl group fatty acyl amido benzene sulfonic acid sodium salt to be dissolved in deionized water, is uniformly mixed, makes shape
At the microemulsion system of 1.0M, then, adding mass fraction is the pH value of 20% tartaric acid regulation system to 6.5, makes system
It is weakly acidic, it is spare.
Take the microemulsion that 50mL is above-mentioned, then add 0.02moL 3,4-rthylene dioxythiophene monomer and 0.2g copper nitrate into
Row stirring and ultrasonic disperse are uniform, then, then oxidant p-methyl benzenesulfonic acid ferrous solution is slowly added dropwise under stirring (makes 3,4-
The molar ratio of ethene dioxythiophene and p-methyl benzenesulfonic acid iron is 1:0.5) and it is slowly added to excessive iron powder simultaneously, wait drip it
After be stirred for reaction 12h, the reaction temperature of control system is 0~6 DEG C in entire reaction process, and it is mixed that suction filtration obtains corresponding solid
Object is closed, then into solid mixture is slowly added to dilute hydrochloric acid and washs to filtrate be in neutrality, finally with a large amount of deionized water, ethyl alcohol
It is centrifuged repeatedly washing, obtains cavernous hollow conductive metal/conductive polymer nanometer pipe.
Cavernous hollow conductive metal/conductive polymer nanometer pipe obtained above and elemental sulfur is taken (to make the matter of the two
Amount is uniformly mixed it than carrying out grinding in mortar for 1:4) mixture, is subsequently placed in the reaction kettle full of argon gas or nitrogen
In, then reaction kettle is put into Muffle furnace, it is heated up with the speed that heating rate is 4 DEG C/min, and control perseverance of the temperature at 155 DEG C
Under the conditions of temperature after high temperature sintering processing 15h, then under 282 DEG C of constant temperature 3h is handled, finally, cooled to room temperature obtains
Lithium sulfur battery anode material.
Performance test after obtained material to be carried out to battery assembly, wherein battery assembly and test are as follows:
It chooses the above-mentioned sulphur anode composite material of 0.8g, 0.1g acetylene black and 0.1g Kynoar and is added to N- methylpyrrole
It is stirred dispersion in alkanone and obtains anode sizing agent, slurry coating is dried to obtain battery anode slice, and using lithium piece as cathode, uses
Celgard2400 diaphragm is added dropwise 25 μ l electrolyte, CR2032 button cell is assembled into glove box and is tested accordingly.
Specifically: make charge and discharge blanking voltage 1.7V~2.8V (vs.Li/Li+)。
Under 0.5C charge and discharge carry out cycle performance test, the composite material its show good cycle performance.This is multiple
The first discharge specific capacity for the respective battery that condensation material obtains reaches 952mAh g-1, coulombic efficiency reaches 98.5%, by 100
Secondary circulation volume is maintained at 521mAh g-1, coulombic efficiency reaches 80.1%.
Embodiment 4
It takes a certain amount of sulphation natrium ricinoleicum to be dissolved in deionized water, is uniformly mixed, make the micro emulsion to form 0.5M
Then liquid system adds the pH value of tartaric acid regulation system to 6.0, keeps system weakly acidic, spare.
Take the microemulsion that 50mL is above-mentioned, then add 0.02moL 3,4-rthylene dioxythiophene monomer and 2.82g copper nitrate into
Row stirring and ultrasonic disperse are uniform, then, then oxidant cerous sulfate solution is slowly added dropwise under stirring (makes 3,4- ethylene two
The molar ratio of oxygen thiophene monomer and cerous sulfate is 1:2) and it is slowly added to excessive iron powder simultaneously, it is anti-wait be stirred for after dripping
14h is answered, the reaction temperature of control system is 6~10 DEG C in entire reaction process, it filters and obtains corresponding solid mixture, then to
It is slowly added to lemon acid elution to filtrate in solid mixture to be in neutrality, is finally centrifuged repeatedly with a large amount of deionized water, ethyl alcohol
Washing, obtains cavernous hollow conductive metal/conductive polymer nanometer pipe.
Cavernous hollow conductive metal/conductive polymer nanometer pipe obtained above and elemental sulfur is taken (to make the matter of the two
Amount is uniformly mixed it than carrying out grinding in mortar for 1:4) mixture, is subsequently placed in the reaction kettle full of argon gas or nitrogen
In, then reaction kettle is put into Muffle furnace, it is heated up with the speed that heating rate is 4 DEG C/min, and control perseverance of the temperature at 200 DEG C
Under the conditions of temperature after high temperature sintering processing 10h, then it is warming up to temperature control and handles 5h, heating speed under 400 DEG C of constant temperature
Rate is 10 DEG C/min, finally, cooled to room temperature obtains lithium sulfur battery anode material.
Performance test after obtained material to be carried out to battery assembly, wherein battery assembly and test are as follows:
It chooses the above-mentioned sulphur anode composite material of 0.8g, 0.1g acetylene black and 0.1g Kynoar and is added to N- methylpyrrole
It is stirred dispersion in alkanone and obtains anode sizing agent, slurry coating is dried to obtain battery anode slice, and using lithium piece as cathode, uses
Celgard2400 diaphragm is added dropwise 25 μ l electrolyte, CR2032 button cell is assembled into glove box and is tested accordingly.
Specifically: make charge and discharge blanking voltage 1.7V~2.8V (vs.Li/Li+)。
Under 0.5C charge and discharge carry out cycle performance test, the composite material its show good cycle performance.This is multiple
The first discharge specific capacity for the respective battery that condensation material obtains reaches 948mAh g-1, coulombic efficiency reaches 98.4%, by 100
Secondary circulation volume is maintained at 531mAh g-1, coulombic efficiency reaches 80.3%.
Specific embodiment described in the present invention only illustrate the spirit of the present invention by way of example.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited
For technical staff, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of preparation method of lithium sulfur battery anode material, which is characterized in that method includes the following steps:
A, anionic surfactant is added in solvent and is configured to microemulsion, acid reagent tune pH value, which is added, makes system in acid
Property；
B, conducting polymer monomer and metal salt are added into microemulsion, then, be added oxidant and excessive metal powder into
Row reaction, after reaction, is collected by filtration solid mixture, then acid solution is added into solid mixture and is washed till filtrate and is in neutrality
Or faintly acid, after then being washed with water or alcohol, obtain corresponding cellular conductive nano metal/conducting polymer composite material；
C, high temperature sintering processing is carried out after mixing conductive metal/conducting polymer composite material and elemental sulfur, is obtained corresponding
Lithium sulfur battery anode material.
2. the preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that metal described in step B
Powder is selected from one or more of aluminium powder, magnesium powder, iron powder and copper powder.
3. the preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that metal described in step B
Salt is selected from one or more of copper nitrate, copper sulphate, copper chloride, silver nitrate and chlorauride.
4. the preparation method of lithium sulfur battery anode material according to claim 1, which is characterized in that acid described in step B is molten
Liquid is one in hydrochloric acid, nitric acid, sulfuric acid, hypochlorous acid, perchloric acid, formic acid, acetic acid, malonic acid, tartaric acid, benzoic acid and citric acid
Kind is a variety of.
5. the preparation method of according to claim 1 or 2 or 3 lithium sulfur battery anode materials, which is characterized in that institute in step B
The mass ratio for stating conducting polymer monomer and metal salt is 20:1~1:2.
6. the preparation method of according to claim 1 or 2 or 3 lithium sulfur battery anode materials, which is characterized in that institute in step B
It is one or more in 3,4-- ethene dioxythiophene, pyrroles, aniline, thiophene and acetylene to state conducting polymer monomer.
7. the preparation method of according to claim 1 or 2 or 3 lithium sulfur battery anode materials, which is characterized in that institute in step B
It is molten selected from sodium peroxydisulfate solution, potassium persulfate solution, ammonium persulfate solution, ferric chloride solution, p-methyl benzenesulfonic acid iron to state oxidant
It is one or more in liquid and cerous sulfate solution；The temperature of reaction described in step B is -20~100 DEG C.
8. the preparation method of according to claim 1 or 2 or 3 lithium sulfur battery anode materials, which is characterized in that described in step A
Anionic surfactant is selected from carboxylate surfactant, sulfonate surfactant, sulfuric ester salt form surface-active
It is one or more in agent and phosphate salt form surfactant.
9. the preparation method of lithium sulfur battery anode material according to claim 7, which is characterized in that the carboxylic acid type surface
Activating agent is selected from one or more of higher fatty acid salt, tri ethanol ammonium salt and N- oleoyl polypeptide；The sulfonate type table
Face activating agent is selected from 2- sodium naphthalene sulfonate, neopelex, dodecane sulfonate, N- oleoyl N-methyl sodium taurocholate
With to one or more of methoxyl group fatty acyl amido benzene sulfonic acid sodium salt；The sulfuric ester salt form surfactant is selected from sulphation
One or both of natrium ricinoleicum, cycloalkanes sodium sulphate；The phosphate salt form surfactant is selected from alkyl phosphoric acid list and alkane
One or both of base phosphate diester salt.
10. the preparation method of according to claim 1 or 2 or 3 lithium sulfur battery anode materials, which is characterized in that institute in step C
State high temperature sintering processing specifically: first control temperature in 100~200 DEG C of constant temperature and handle 2~48h, then, then control temperature and exist
200~400 DEG C of constant temperature handle 1~10h, finally, cooled to room temperature, obtains sulphur anode composite material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110350142A (en) * | 2019-06-28 | 2019-10-18 | 浙江大学 | The sodium electrode of integrated Porous Polypyrrole load and the preparation method of sulfur electrode |
| CN110371950A (en) * | 2019-08-12 | 2019-10-25 | 苏州大学 | A kind of preparation method of hollow carbon material |
| CN111969194A (en) * | 2020-08-27 | 2020-11-20 | 广东工业大学 | Battery positive electrode material and preparation method and application thereof |
| CN114592185A (en) * | 2020-12-07 | 2022-06-07 | 中国科学技术大学 | Metal composite material plated with conductive metal and preparation method and application thereof |
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