CN107069002B - A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell - Google Patents
A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell Download PDFInfo
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- CN107069002B CN107069002B CN201710228736.8A CN201710228736A CN107069002B CN 107069002 B CN107069002 B CN 107069002B CN 201710228736 A CN201710228736 A CN 201710228736A CN 107069002 B CN107069002 B CN 107069002B
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell.Lithium sulfur battery anode material provided by the invention includes carbon hollow ball, the nano-titanium dioxide for being attached to the carbon hollow ball surfaces externally and internally and the sulphur simple substance being filled in the carbon hollow ball, and the mass content of the sulphur simple substance is 60~80%.The experimental results showed that the lithium-sulfur cell of lithium sulfur battery anode material preparation provided by the invention is at 1C, discharge capacity still keeps 691mAhg after 200 circulations‑1, 300 times circulation after discharge capacity still keep 671mAhg‑1, coulombic efficiency is maintained at 97% or so；Under 4C high rate cyclic, discharge capacity is still able to maintain 527mAhg‑1, when turning again to 1C, discharge capacity can still keep 1042mAhg‑1。
Description
Technical field
The present invention relates to technical field of function materials, in particular to a kind of lithium sulfur battery anode material and preparation method thereof and
Lithium-sulfur cell.
Background technique
With the day and night growth of auto output, petroleum resources are petered out, and environmental pollution is on the rise, and are badly in need of exploitation
Renewable energy replaces energy supply system, especially electrochemical energy storage system before this.Lithium ion battery is current comprehensive performance
Best secondary cell system is studied by the effort in common people's nearly twenty or thirty year, and the capacity of lithium ion battery plus-negative plate material is equal
Its theoretical limit is had been approached, however is still difficult to meet the needs of energy-storage system is day and night gradually grown.Therefore, it is necessary to develop new energy is close
The electrode material of degree come meet society power demand.
Lithium-sulfur cell is a kind of lithium battery of the lithium metal as battery cathode using element sulphur as anode, theoretical
Specific capacity and specific energy are all higher, respectively 1672mAh/g and 2600Wh/kg.Wherein elemental sulfur earth rich reserves, price are low
It is honest and clean, advantages of environment protection.But lithium-sulfur cell there is a problem of three it is serious: (1) sulphur electric conductivity is excessively poor, reaction it is final
Product Li2S2And Li2S is insulator, is unfavorable for battery high rate capability；(2) the intermediate discharging product of lithium-sulfur cell vulcanizes conjunction more
Object can be dissolved into electrolyte, and reduce ionic conductivity, in the migration of positive and negative interpolar, will lead to the loss of active material；
(3) for sulphur in charge and discharge process, volume change is big, battery easy to damage.
To solve the above-mentioned problems, the modification of positive sulphur is particularly important.The prior art is mainly by sulphur and conduction
Basis material it is compound, such as: conductive carbon material (porous carbon, carbon nanotube, graphene or graphene oxide), high molecular polymerization
Object (polypyrrole, polyaniline, polythiophene or polyethylene dioxy thiophene) and metal oxide materials (MnO2、ZnO、Ni(OH)2、
MgXNi1-XO or TiO2), positive conductive is assigned by conductive material, inhibits sulfide shuttle effect, to improve following for battery
Ring performance and high rate performance.But dissolution and shuttle effect of the positive electrode in above-mentioned technical proposal for polysulfide
Inhibiting effect is limited, and the improvement of cycle performance and high rate performance for lithium-sulfur cell is not obvious.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cells.The present invention
The lithium sulfur battery anode material of offer can effectively inhibit the volume change of sulphur and the dissolution of polysulfide and shuttle effect, from
And improve the cycle performance and high rate performance of lithium-sulfur cell.
The present invention provides a kind of lithium sulfur battery anode material, including carbon hollow ball, it is attached to inside and outside the carbon hollow ball
The nano-titanium dioxide on surface and the sulphur simple substance being filled in the carbon hollow ball, the mass content of the sulphur simple substance is 60~
80%.
Preferably, the internal diameter of the carbon hollow ball is 150~350nm, and outer diameter is 200~400nm.
Preferably, the partial size of the lithium sulfur battery anode material is 250~450nm.
The present invention also provides the preparation methods of lithium sulfur battery anode material described in above-mentioned technical proposal, including following step
It is rapid:
(1) nanometer titanium dioxide silicon suspension is mixed with nano-titanium dioxide, obtains mixing suspension；
(2) surfactant, phenols, formaldehyde and catalysis are sequentially added in the mixing suspension that Xiang Suoshu step (1) obtains
Agent, polycondensation reaction obtain the first presoma；
(3) the first presoma that the step (2) obtains is mixed with mixed solvent, tetraethyl orthosilicate, hydrolysis is added
Reaction obtains the second presoma；
(4) it is performed etching after calcining the second presoma that the step (3) obtains, obtains titanium dioxide-carbon hollow ball
Compound；The titanium dioxide-carbon hollow ball compound includes carbon hollow ball and is attached to the carbon hollow ball surfaces externally and internally
Nano-titanium dioxide；
(5) hot place is carried out after mixing titanium dioxide-carbon hollow ball compound that the step (4) obtains with sulphur simple substance
Reason, obtains lithium sulfur battery anode material.
Preferably, the temperature of polycondensation reaction is 0~100 DEG C in the step (2), and the time of polycondensation reaction is 1~48h.
Preferably, the calcining in the step (4) successively includes low temperature calcination and high-temperature calcination, the temperature of the low temperature calcination
Degree is 200~550 DEG C.
Preferably, the time of the low temperature calcination is 0.5~8h.
Preferably, the temperature of the high-temperature calcination is 600~1200 DEG C, and the time of high-temperature calcination is 0.5~12h.
Preferably, the temperature being heat-treated in the step (5) is 120~180 DEG C, the time of heat treatment is 3~for 24 hours.
The present invention also provides a kind of lithium-sulfur cell, including anode, cathode of lithium and electrolyte, the anode includes active matter
Matter, the active material is for lithium sulfur battery anode material described in above-mentioned technical proposal or according to preparation side described in above-mentioned technical proposal
The lithium sulfur battery anode material of method preparation.
The present invention provides a kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cells.Lithium provided by the invention
Sulphur cell positive electrode material includes carbon hollow ball, the nano-titanium dioxide for being attached to the carbon hollow ball surfaces externally and internally and is filled in
Sulphur simple substance in the carbon hollow ball, the mass content of the sulphur simple substance are 60~80%.Lithium-sulfur cell provided by the invention is just
Pole material has stable shape with carbon hollow ball and nanometer titanium dioxide-coated sulphur simple substance, carbon hollow ball, effectively alleviates and puts
The variation of sulphur pressure and volume in electricity/charging process, and there is good electric conductivity, make up the insulating properties of sulphur；Nanometer titanium dioxide
Titanium has chemisorption to sulphur and polysulfide, on the one hand can effectively alleviate sulphur pressure and volume during charged/discharged
Variation, on the other hand can effectively inhibit the shuttle effect of polysulfide；In addition, carbon hollow ball has with nano-titanium dioxide
Synergistic effect cooperates sulfur content appropriate, and hollow sphere/titanium dioxide-sulphur composite construction is enable to promote electron-transport simultaneously
And the low conductive sulphur that is quickly transferred to of lithium ion is protected, and then the high rate performance and cyclical stability of raising lithium-sulfur cell.Experiment
The result shows that the lithium-sulfur cell of lithium sulfur battery anode material provided by the invention preparation is at 1C, discharge capacity after 200 circulations
Still keep 691mAhg-1, 300 times circulation after discharge capacity still keep 671mAhg-1, coulombic efficiency is maintained at 97% or so；
Under 4C high rate cyclic, discharge capacity is still able to maintain 527mAhg-1, when turning again to 1C, discharge capacity can still be kept
1042mAh·g-1。
Detailed description of the invention
Fig. 1 is the preparation principle schematic diagram of lithium sulfur battery anode material of the present invention；
Fig. 2 is the stereoscan photograph of lithium sulfur battery anode material in the embodiment of the present invention 1；
Fig. 3 is the distribution diagram of element of lithium sulfur battery anode material in the embodiment of the present invention 1, wherein a is SEM figure, and b is C member
Plain distribution map, c are Ti distribution diagram of element, and d is S distribution diagram of element；
Fig. 4 is the charging and discharging curve of lithium-sulfur cell in the embodiment of the present invention 2；
Fig. 5 is the high rate performance figure of lithium-sulfur cell in the embodiment of the present invention 2；
Fig. 6 is the cycle performance figure of lithium-sulfur cell in the embodiment of the present invention 2.
Specific embodiment
The present invention provides a kind of lithium sulfur battery anode material, including carbon hollow ball, it is attached to inside and outside the carbon hollow ball
The nano-titanium dioxide on surface and the sulphur simple substance being filled in the carbon hollow ball, the mass content of the sulphur simple substance is 60~
80%.
Lithium sulfur battery anode material provided by the invention includes carbon hollow ball.In the present invention, the carbon hollow ball is interior
Diameter is preferably 150~350nm, more preferably 170~320nm, most preferably 200~300nm；The outer diameter of the carbon hollow ball is excellent
It is selected as 200~400nm, more preferably 220~350nm, most preferably 250~300nm.The present invention contains the carbon hollow ball
Not special restriction is measured, sulphur simple substance can be coated.In the present invention, the mass content of the carbon hollow ball is preferably 10
~35%, more preferably 15~30%, most preferably 20~25%.In the present invention, the carbon hollow ball has stable shape
Shape, effectively alleviates the variation of sulphur pressure and volume during charged/discharged, and has good electric conductivity, makes up the exhausted of sulphur
Edge.
Lithium sulfur battery anode material provided by the invention includes the nano-silica for being attached to the carbon hollow ball surfaces externally and internally
Change titanium.In the present invention, the partial size of the nano-titanium dioxide is preferably 20~40nm, more preferably 25~35nm.In this hair
In bright, the nano-titanium dioxide preferably has rutile structure.The present invention is to the nano-titanium dioxide in carbon hollow ball
The distribution density of outer surface does not have special restriction, is uniformly distributed it i.e. according to the content of nano-titanium dioxide and carbon hollow ball
It can.In the present invention, the mass ratio of the nano-titanium dioxide of the carbon hollow ball surfaces externally and internally is preferably 1~5%, more preferably
2~3%.In the present invention, the mass content of the nano-titanium dioxide is preferably 4~15%, and more preferably 6~12%, most
Preferably 8~10%.In the present invention, the nano-titanium dioxide has chemisorption to sulphur and polysulfide, on the one hand can be with
Effectively alleviate charged/discharged during sulphur pressure and volume variation, on the other hand can effectively inhibit polysulfide
Shuttle effect.
Lithium sulfur battery anode material provided by the invention includes the sulphur simple substance being filled in the carbon hollow ball, the sulphur list
The mass content of matter is 60~80%, preferably 64~76%, more preferably 67~72%.The present invention is to the sulphur simple substance in carbon
Compactedness in hollow sphere does not have special restriction, is adjusted according to the content of sulphur simple substance.In the present invention, the spy
Active material of the sulphur simple substance as positive electrode for determining content, in the synergistic effect of the carbon hollow ball and nano-titanium dioxide
Under, so that hollow sphere/titanium dioxide-sulphur composite construction is promoted electron-transport simultaneously and is protected being quickly transferred to for lithium ion
Low conduction sulphur, and then improve the high rate performance and cyclical stability of lithium-sulfur cell.
In the present invention, the partial size of the lithium sulfur battery anode material is preferably 250~450nm, more preferably 280~
420nm, most preferably 310~390nm.
The present invention also provides the preparation methods of lithium sulfur battery anode material described in above-mentioned technical proposal, including following step
It is rapid:
(1) nanometer titanium dioxide silicon suspension is mixed with nano-titanium dioxide, obtains mixing suspension；
(2) surfactant, phenols, formaldehyde and catalysis are sequentially added in the mixing suspension that Xiang Suoshu step (1) obtains
Agent, polycondensation reaction obtain the first presoma；
(3) the first presoma that the step (2) obtains is mixed with mixed solvent, tetraethyl orthosilicate, hydrolysis is added
Reaction obtains the second presoma；
(4) it is performed etching after calcining the second presoma that the step (3) obtains, obtains titanium dioxide-carbon hollow ball
Compound；The titanium dioxide-carbon hollow ball compound includes carbon hollow ball and is attached to the carbon hollow ball surfaces externally and internally
Nano-titanium dioxide；
(5) hot place is carried out after mixing titanium dioxide-carbon hollow ball compound that the step (4) obtains with sulphur simple substance
Reason, obtains lithium sulfur battery anode material.
The preparation principle schematic diagram of lithium sulfur battery anode material of the present invention is as shown in Figure 1.In nano-silica surface packet
Titanium dioxide nanoparticle is covered, silica-titania compound is formed；In the nano silica-nanometer titanium dioxide
Titanium composite surface coats phenolic resin, and then coated silica forms protective layer, makes phenolic resin carbonized through calcining, then pass through
Etching removal silica, obtains titanium dioxide-carbon hollow ball compound；Finally by heat treatment, sulphur simple substance is packed into carbon
In hollow sphere, lithium sulfur battery anode material is obtained.
The present invention mixes nanometer titanium dioxide silicon suspension with nano-titanium dioxide, obtains mixing suspension.In the present invention
In, the mass ratio of nano silica and nano-titanium dioxide is preferably 1:0.1~10 in the mixing suspension, more preferably
1:0.2~5, most preferably 1:0.5~2.
The not special restriction of the operation that the present invention mixes the nanometer titanium dioxide silicon suspension with nano-titanium dioxide,
Using the technical solution well known to those skilled in the art for preparing dispersion liquid.In the present invention, the nano silica
The temperature that suspension is mixed with nano-titanium dioxide is preferably 0~80 DEG C, more preferably 20~50 DEG C, most preferably 25~30
℃.In the present invention, the mixing of the nanometer titanium dioxide silicon suspension and nano-titanium dioxide preferably carries out under agitation；
The stirring is preferably magnetic agitation；The rate of the stirring is preferably 6000~10000r/min, more preferably 7000~
9000r/min；The time of the stirring is preferably 0.2~10h, more preferably 0.5~8h, most preferably 1~5h.In the present invention
In, the mixing of the nanometer titanium dioxide silicon suspension and nano-titanium dioxide makes nano-titanium dioxide uniformly be attached to nano-silica
The surface of SiClx.
In the present invention, the mass ratio of the nano silica in the nanometer titanium dioxide silicon suspension and solvent is preferably
1:20~500, more preferably 1:50~400, most preferably 1:100~300.In the present invention, the nano silica
Partial size is preferably 20~40nm, more preferably 25~35nm.In the present invention, the solvent of the nanometer titanium dioxide silicon suspension is excellent
It is selected as the mixed solvent of alcohol and water；The mass ratio of the alcohol and water is preferably 0.1~5:1, more preferably 0.5~3:1, most preferably
For 1~2:1.
The present invention does not have special restriction to the type of the alcohol, is using alcohols solvent well known to those skilled in the art
It can.In the present invention, the alcohol is preferably one in methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, propylene glycol and glycerine
Kind is a variety of.
The present invention restriction not special to the operation of the preparation of the nanometer titanium dioxide silicon suspension, using this field skill
The technical solution of dispersion liquid is prepared known to art personnel.The present invention preferably mixes nano silica with solvent, obtains
Nanometer titanium dioxide silicon suspension.
The present invention does not have special restriction to the source of the nano silica, and use is well known to those skilled in the art
Commercial product, or prepared according to the preparation method of nano silica well known to those skilled in the art.In the present invention,
The preparation of the nano silica preferably includes following steps: alcohol, ammonium hydroxide and water being mixed, mixed solvent is obtained；It will be described
Mixed solvent is mixed with tetraethyl orthosilicate, and hydrolysis obtains nano silica.
The present invention preferably mixes alcohol, ammonium hydroxide and water, obtains mixed solvent.The present invention mixes the alcohol, ammonium hydroxide and water
The not special restriction of operation, using the technical solution well known to those skilled in the art for preparing mixed solvent.At this
In invention, the mass concentration of the ammonium hydroxide is preferably 25~28%, and more preferably 26~27%.In the present invention, the alcohol, ammonia
The mass ratio of water and water is preferably 2~15:0.1~5:1, more preferably 5~12:0.5~3:1, most preferably 8~10:1~2:
1.The present invention does not have special restriction to the type of the alcohol, using alcohols solvent well known to those skilled in the art.?
In the present invention, the alcohol be preferably one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, propylene glycol and glycerine or
It is a variety of.
After obtaining mixed solvent, the present invention preferably mixes the mixed solvent with tetraethyl orthosilicate, and hydrolysis obtains
To nano silica.In the present invention, the mass content of silica is preferably 20% or more in the tetraethyl orthosilicate,
More preferably 28% or more.In the present invention, the mass ratio of the tetraethyl orthosilicate and mixed solvent is preferably 1:1~100,
More preferably 1:10~80, most preferably 1:20~50.In order to slow down the decomposition rate of tetraethyl orthosilicate, silica is avoided
Agglomerating or diameter is excessive, and the tetraethyl orthosilicate is preferably rapidly injected in the mixed solvent by the present invention；The positive silicic acid tetrem
The charge velocity of ester is preferably 1~2mL/s.
It is somebody's turn to do in the present invention, the temperature of the hydrolysis is preferably 0~100 DEG C, and more preferably 20~80 DEG C, most preferably
It is 25~50 DEG C；The time of the hydrolysis is preferably 0.1~5h, more preferably 0.5~3h, most preferably 1~2h.
After the completion of hydrolysis, the product of the hydrolysis is preferably separated by solid-liquid separation by the present invention, then will separation
Obtained solid is dry, obtains nano silica.The present invention limit not special to the separation of solid and liquid and dry operation
It is fixed, using separation of solid and liquid well known to those skilled in the art and dry technical solution.In the present invention, the solid-liquid point
From preferably centrifugation；The rate of the centrifugation is preferably 7000~9000r/min, more preferably 7500~8500r/min；It is described
The time of centrifugation is preferably 4~8min, more preferably 5~7min.
The not special restriction of operation of the present invention to the drying, using the skill of drying well known to those skilled in the art
Art scheme.In the present invention, the drying is preferably dried in vacuo；The vacuum drying vacuum degree is preferably 0.02~
0.15MPa；More preferably 0.05~0.1MPa；The vacuum drying temperature is preferably 40~120 DEG C, more preferably 60~
100 DEG C, most preferably 70~90 DEG C；The vacuum drying time is preferably 1~96h, more preferably 10~80h, most preferably
For 30~50h.
After obtaining mixing suspension, the present invention will sequentially add surfactant, phenols, formaldehyde in the mixing suspension
And ammonium hydroxide, polycondensation reaction obtain the first presoma.In the present invention, the charging sequence can make phenols and formaldehyde in nanometer two
Silica and nano-titanium dioxide surface carry out polycondensation reaction, and the phenolic resin for obtaining polycondensation reaction is coated on nanometer titanium dioxide
Silicon and nano-titanium dioxide surface are to get arriving presoma one.
In the present invention, the surfactant is preferably cetyl trimethylammonium bromide, cetyl trimethyl chlorine
Change ammonium or dodecyl trimethyl ammonium bromide.In the present invention, the phenols is preferably resorcinol, catechol and to benzene two
One or more of phenol.In the present invention, the formaldehyde is preferably the aqueous solution of formaldehyde；The quality of the formalin is dense
Degree preferably 37~40%, more preferably 38~39%.In the present invention, the mass concentration of the ammonium hydroxide be preferably 25~
28%, more preferably 26~27%.
In the present invention, the nano silica in the mixing suspension and surfactant, phenols, formalin
Mass ratio with ammonium hydroxide is preferably 1:0.05~10:0.05~10:0.05~10:0.1~15, more preferably 1:0.1~5:0.1
~5:0.1~5:0.5~10, most preferably 1:0.5~3:0.5~3:0.5~3:1~5.
In the present invention, the temperature of the polycondensation reaction is preferably 0~100 DEG C, and more preferably 20~80 DEG C, most preferably
25~50 DEG C；The time of the polycondensation reaction is preferably 1~48h, more preferably 5~40h, most preferably 10~20h.
After the completion of polycondensation reaction, product of the present invention preferably by the polycondensation reaction is separated by solid-liquid separation, then will separation
Obtained solid is dry, obtains the first presoma.The present invention restriction not special to the separation of solid and liquid and dry operation,
Using separation of solid and liquid well known to those skilled in the art and dry technical solution.In the present invention, the separation of solid and liquid
Preferably it is centrifuged；The rate of the centrifugation is preferably 7000~9000r/min, more preferably 7500~8500r/min；It is described from
The time of the heart is preferably 4~8min, more preferably 5~7min.
The not special restriction of operation of the present invention to the drying, using the skill of drying well known to those skilled in the art
Art scheme.In the present invention, the drying is preferably dried in vacuo；The vacuum drying vacuum degree is preferably 0.02~
0.15MPa；More preferably 0.05~0.1MPa；The vacuum drying temperature is preferably 40~120 DEG C, more preferably 60~
100 DEG C, most preferably 70~90 DEG C；The vacuum drying time is preferably 1~96h, more preferably 10~80h, most preferably
For 30~50h.
After obtaining the first presoma, the present invention mixes first presoma with mixed solvent, and positive silicic acid tetrem is added
Ester, hydrolysis obtain the second presoma.In the present invention, the mixed solvent preferably includes alcohol, ammonium hydroxide and water.In the present invention
In, the alcohol is preferably one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, propylene glycol and glycerine or a variety of.?
In the present invention, the mass concentration of the ammonium hydroxide is preferably 25~28%, and more preferably 26~27%.In the present invention, the alcohol,
The mass ratio of ammonium hydroxide and water be preferably 2~15:0.01~1:1, more preferably 5~12:0.05~0.8:1, most preferably 8~
10:0.1~0.5:1.
In the present invention, the mass content of silica is preferably 20% or more in the tetraethyl orthosilicate, more preferably
It is 28% or more.In the present invention, the mass ratio of first presoma, mixed solvent and tetraethyl orthosilicate is preferably 1:50
~200:0.1~10, more preferably 1:100~150:1~5.
The not special restriction of the operation that the present invention mixes first presoma with mixed solvent, using this field skill
The technical solution of dispersion liquid is prepared known to art personnel.In the present invention, the adding manner of the tetraethyl orthosilicate is excellent
It is selected as injecting；The rate of the injection is preferably 1~2mL/s.In the present invention, the temperature of the hydrolysis be preferably 0~
100 DEG C, more preferably 20~80 DEG C, most preferably 25~50 DEG C；The time of hydrolysis is preferably 0.1~5h, and more preferably 1
~4h, most preferably 2~3h.
In the present invention, it is preferred to start the process terminated to hydrolysis for the mixing of first presoma and mixed solvent
It carries out under agitation；The stirring is preferably magnetic agitation；The rate of the stirring is preferably 7000~9000r/min,
More preferably 7500~8500r/min.In the present invention, the hydrolysis forms silica packet on the first presoma surface
Coating, obtains the second presoma, and the coated with silica layer has the function that robust structure during subsequent calcination, avoids
Structure collapses when subsequent calcination.
After obtaining the second presoma, the present invention performs etching after calcining second presoma, obtains titanium dioxide-carbon
Hollow sphere compound；The titanium dioxide-carbon hollow ball compound includes carbon hollow ball and is attached to inside and outside the carbon hollow ball
The nano-titanium dioxide on surface.In the present invention, the calcining preferably successively includes low temperature calcination and high-temperature calcination.In the present invention
In, the temperature of the low temperature calcination is preferably 200~550 DEG C, more preferably 300~500 DEG C, most preferably 350~450 DEG C；
The time of the low temperature calcination is preferably 0.5~8h, more preferably 1~5h, most preferably 2~3h.In the present invention, the height
The temperature of temperature calcining is preferably 600~1200 DEG C, more preferably 800~1000 DEG C, most preferably 850~950 DEG C；The high temperature
The time of calcining is preferably 0.5~12h, more preferably 1~10h, most preferably 3~6h.In the present invention, the calcining is preferred
It carries out under inert gas protection；The inert gas is preferably argon gas or nitrogen.The present invention is warming up to the low temperature calcination
The heating rate of high-temperature calcination does not have special restriction, using heating rate well known to those skilled in the art.In this hair
In bright, the low temperature calcination carries out carbonization pre-treatment to substance；In the high-temperature burning process, it is empty that phenolic resin carbonized forms carbon
Bulbus cordis.
After the completion of calcining, the present invention performs etching the product of the calcining, and it is compound to obtain titanium dioxide-carbon hollow ball
Object.In the present invention, the time of the etching is preferably 1~72h, more preferably 10~60h, most preferably 20~40h.At this
In invention, the etching is preferred specifically: mixes the product of calcining with sodium hydroxide solution.In the present invention, the hydrogen-oxygen
The molar concentration for changing sodium solution is preferably 0.1~15mol/L, more preferably 1~10mol/L, most preferably 3~5mol/L.
After the completion of etching, the product of the etching is preferably separated by solid-liquid separation by the present invention, then consolidates isolated
Soma is dry, obtains titanium dioxide-carbon hollow ball compound.The present invention is not special to the separation of solid and liquid and dry operation
It limits, using separation of solid and liquid well known to those skilled in the art and dry technical solution.In the present invention, the solid-liquid
Separation is preferably centrifuged；The rate of the centrifugation is preferably 7000~9000r/min, more preferably 7500~8500r/min；Institute
The time for stating centrifugation is preferably 4~8min, more preferably 5~7min.
The not special restriction of operation of the present invention to the drying, using the skill of drying well known to those skilled in the art
Art scheme.In the present invention, the drying is preferably dried in vacuo；The vacuum drying vacuum degree is preferably 0.02~
0.15MPa；More preferably 0.05~0.1MPa；The vacuum drying temperature is preferably 40~120 DEG C, more preferably 60~
100 DEG C, most preferably 70~90 DEG C；The vacuum drying time is preferably 1~96h, more preferably 10~80h, most preferably
For 30~50h.
After obtaining titanium dioxide-carbon hollow ball compound, the present invention is by the titanium dioxide-carbon hollow ball compound and sulphur
It is heat-treated after simple substance mixing, obtains lithium sulfur battery anode material.In the present invention, the titanium dioxide-carbon hollow ball is multiple
The mass ratio for closing object and sulphur simple substance is preferably 1:0.1~20, more preferably 1:0.5~15, most preferably 1:1~10.
The not special restriction of the operation that the present invention mixes the titanium dioxide-carbon hollow ball compound with sulphur simple substance,
The technical solution mixed using powder well known to those skilled in the art.In the present invention, the titanium dioxide-carbon is hollow
The mixing of ball compound and sulphur simple substance is preferably mixing of milling；The time of the mixing of milling is preferably 0.1~5h, more preferably
0.5~3h, most preferably 1~2h.
In the present invention, the temperature of the heat treatment is preferably 120~180 DEG C, and more preferably 140~160 DEG C, most preferably
It is 145~155 DEG C；The time of the heat treatment is preferably 3~for 24 hours, more preferably 5~20h, most preferably 10~15h.At this
In invention, the heat treatment preferably carries out under inert gas protection；The inert gas is preferably argon gas or nitrogen.In this hair
In bright, the heat treatment is packed into sulphur simple substance in carbon hollow ball, effectively alleviates sulphur pressure and body during charged/discharged
Long-pending variation.
The present invention also provides a kind of lithium-sulfur cell, including anode, cathode of lithium and electrolyte, the anode includes active matter
Matter, the active material is for lithium sulfur battery anode material described in above-mentioned technical proposal or according to preparation side described in above-mentioned technical proposal
The lithium sulfur battery anode material of method preparation.In the present invention, the anode preferably includes lithium-sulfur cell described in above-mentioned technical proposal
Positive electrode, carbon black and polyvinylidene fluoride.The present invention does not have special restriction to the type of the cathode of lithium and electrolyte, adopts
With the cathode of lithium and electrolyte of lithium-sulfur cell well known to those skilled in the art.
The present invention does not have special restriction to the preparation method of the lithium-sulfur cell, and use is well known to those skilled in the art
Assemble the technical solution of lithium-sulfur cell.
In order to further illustrate the present invention, below with reference to embodiment to lithium sulfur battery anode material provided by the invention and its
Preparation method and lithium-sulfur cell are described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1:
It prepares mixed solution (75mL ethyl alcohol+3.2mL ammonium hydroxide (26wt%)+10mL deionized water), in the item of lasting stirring
Under part, 6ml tetraethyl orthosilicate is added rapidly in above-mentioned solution in 3s, 1h is reacted at 20 DEG C, separate solid product and is done
It is dry, obtain the silica that partial size is 250nm；
The mixing that the titanium dioxide of silica obtained and 2.5g is dispersed in 130mL deionized water and 50mL ethyl alcohol is molten
In agent, 20min is stirred at 20 DEG C；Then sequentially add 0.8g cetyl trimethylammonium bromide, 0.35g resorcinol,
The formaldehyde of 0.5mL and the ammonium hydroxide (26wt%) of 2mL react 15h under the conditions of 30 DEG C, solid product and drying are separated, before obtaining
Drive body one；
Presoma one is distributed to 75mL ethyl alcohol, the mixed solution of 10mL deionized water and 3.2mL ammonium hydroxide (26wt%),
Under conditions of stirring, it is added rapidly to above-mentioned solution in the tetraethyl orthosilicate 3s of 3mL, separates solid product and drying, obtains
Presoma two；
Finally under the protection of argon gas after 350 DEG C of calcining 2h, continuation calcines 4h under the conditions of 800 DEG C；After product is cooling,
It is added in the 3mol/L sodium hydroxide solution of 10ml, reacts 12h, separate solid product and drying to get titanium dioxide-carbon is arrived
Hollow sphere compound；
Titanium dioxide made from 1g-carbon hollow ball compound is mixed into the 0.5h that mills with 3g sulphur simple substance, in the atmosphere of argon gas
Lower 155 DEG C of calcining 12h to get arrive lithium sulfur battery anode material.
The scanned picture of lithium sulfur battery anode material manufactured in the present embodiment is as shown in Figure 2.Figure it is seen that this reality
The partial size for applying the lithium sulfur battery anode material of example preparation is 300nm.
For the Elemental redistribution of lithium sulfur battery anode material manufactured in the present embodiment as shown in figure 3, wherein a is SEM figure, b is C member
Plain distribution map, c are Ti distribution diagram of element, and d is S distribution diagram of element.From figure 3, it can be seen that carbon is distributed in hollow ball-shape, titanium is in circle
Annular spread, sulphur are in the hollow position of carbon.
The internal diameter of carbon hollow ball is 290nm, outer diameter 300nm, mass content 25%；The partial size of nano-titanium dioxide is
30nm, mass content 8%；The mass content of sulphur is 67%.
Embodiment 2:
The lithium sulfur battery anode material prepared in embodiment 1 is assembled into lithium-sulfur cell: by dioxy obtained by embodiment 1
Change titanium-carbon hollow ball/sulphur is positive electrode, and carbon black (SuperP) is conductive material, and polyvinylidene fluoride is adhesive, current-collector
It is aluminium flake, cathode is lithium piece, and diaphragm is Celgard2400 film, and support chip is spring leaf, and electrolyte is double fluoroforms of 1M
Sulfimide lithium (LiTFSI) is dissolved in 1,3- dioxolane (DOL)/glycol dimethyl ether (DME)=1:1V%, and adds 1%
Lithium nitrate.
The charging and discharging curve of lithium-sulfur cell manufactured in the present embodiment is as shown in Figure 4.From fig. 4, it can be seen that at 1C, battery
Discharge capacity still keeps 691mAhg after 200 circulations-1。
The high rate performance of lithium-sulfur cell manufactured in the present embodiment is as shown in Figure 5.From fig. 5, it can be seen that being followed in 4C high magnification
Under ring, discharge capacity of the cell is still able to maintain 527mAhg-1, when turning again to 1C, discharge capacity can still keep 1042mAhg-1。
The cycle performance of lithium-sulfur cell manufactured in the present embodiment is as shown in Figure 6.From fig. 6, it can be seen that at 1C, battery
Discharge capacity still keeps 671mAhg after 300 circulations-1, coulombic efficiency is maintained at 97% or so.
Embodiment 3:
It prepares mixed solution (100mL methanol+5mL ammonium hydroxide (26wt%)+10mL deionized water), in the condition of lasting stirring
Under, 10ml tetraethyl orthosilicate is added rapidly in above-mentioned solution, 1h is reacted at 30 DEG C, solid product and drying is separated, obtains
The silica for being 260nm to partial size；
The titanium dioxide of nano silica obtained and 5g is dispersed in the mixed of 100mL deionized water and 100mL methanol
In bonding solvent, 15min is stirred at 25 DEG C；Then the catechol of 1.6g cetyl trimethylammonium bromide, 0.7g are sequentially added,
The formaldehyde of 1mL and the ammonium hydroxide (26wt%) of 4mL react for 24 hours under the conditions of 30 DEG C, separate solid product and drying, obtain forerunner
Body one；
Presoma one is distributed to 100mL methanol, the mixed solution of 20mL deionized water and 5mL ammonium hydroxide (26wt%),
Under conditions of stirring, the tetraethyl orthosilicate of 5mL is added rapidly to above-mentioned solution, separates solid product and drying, obtains forerunner
Body two；
Finally under the protection of argon gas after 300 DEG C of calcining 3h, continuation calcines 3h under the conditions of 900 DEG C, after product is cooling,
It is added in the 4mol/L sodium hydroxide solution of 15ml, reaction for 24 hours, separates solid product and drying to get titanium dioxide-carbon is arrived
Hollow sphere compound；
Titanium dioxide made from 2g-carbon hollow ball compound is mixed into the 1h that mills with 5g sulphur simple substance, under the atmosphere of argon gas
155 DEG C of calcining 15h to get arrive lithium sulfur battery anode material.
The partial size of lithium sulfur battery anode material manufactured in the present embodiment is 335nm, and the internal diameter of carbon hollow ball is 300nm, outside
Diameter is 310nm, mass content 25%；The partial size of nano-titanium dioxide is 25nm, mass content 11%；The mass content of sulphur
It is 64%.
Embodiment 4:
The lithium sulfur battery anode material prepared in embodiment 3 is assembled into lithium-sulfur cell in the way of embodiment 2.
Lithium-sulfur cell manufactured in the present embodiment, at 1C, battery discharge capacity after 200 circulations still keeps 596mAh
g-1。
Embodiment 5:
It prepares mixed solution (50mL n-butanol+4mL ammonium hydroxide (26wt%)+30mL deionized water), in the item of lasting stirring
Under part, 5ml tetraethyl orthosilicate is added rapidly in above-mentioned solution, 1h is reacted at 40 DEG C, separates solid product and drying, both
Obtain the silica that partial size is 230nm；
The titanium dioxide that silica obtained and 1g partial size are 25nm is dispersed in 100mL deionized water and the positive fourth of 50mL
The in the mixed solvent of alcohol stirs 10min at 30 DEG C.Then sequentially add 1g cetyl trimethylammonium bromide, 0.5g to benzene
Diphenol, the formaldehyde of 1mL and the ammonium hydroxide (26wt%) of 3mL react 12h under the conditions of 40 DEG C, separate solid product and drying, obtain
Presoma one；
Presoma one is distributed to 100mL n-butanol, the mixed solution of 20mL deionized water and 2mL ammonium hydroxide (26wt%),
Under stirring conditions, the tetraethyl orthosilicate of 10mL is added rapidly to above-mentioned solution, solid product and drying is separated, before obtaining
Drive body two；
Finally under the protection of nitrogen after 400 DEG C of calcining 1h, continuation calcines 5h under the conditions of 700 DEG C, after product is cooling,
It is added in the 2mol/L sodium hydroxide solution of 12ml, reacts 48h, separate solid product and drying to get titanium dioxide-carbon is arrived
Hollow sphere compound；
Titanium dioxide made from 1g-carbon hollow ball compound is mixed into the 0.5h that mills with 2g sulphur simple substance, in the atmosphere of nitrogen
Lower 155 DEG C of calcining 10h to get arrive lithium sulfur battery anode material.
The partial size of lithium sulfur battery anode material manufactured in the present embodiment is 305nm, and the internal diameter of carbon hollow ball is 270nm, outside
Diameter is 280nm, mass content 34%；The partial size of nano-titanium dioxide is 25nm, mass content 5%；The mass content of sulphur
It is 60%.
Embodiment 6:
The lithium sulfur battery anode material prepared in embodiment 5 is assembled into lithium-sulfur cell in the way of embodiment 2.
Lithium-sulfur cell manufactured in the present embodiment, at 1C, battery discharge capacity after 200 circulations still keeps 572mAh
g-1。
Embodiment 7:
It prepares mixed solution (75mL ethyl alcohol+3.2mL ammonium hydroxide (26wt%)+10mL deionized water), in the item of lasting stirring
Under part, 5ml tetraethyl orthosilicate is added rapidly in above-mentioned solution, after reacting 0.5h at 20 DEG C, is further continued for 40 DEG C of reactions
0.5h separates solid product and drying, has both obtained the silica that partial size is 240nm；
The titanium dioxide that silica obtained and 1g partial size are 28nm is dispersed in 100mL deionized water and 50mL ethyl alcohol
In the mixed solvent, stir 10min at 40 DEG C.Then the isophthalic of 0.5g cetyl trimethylammonium bromide, 0.3g are sequentially added
Diphenol, the formaldehyde of 1mL and the ammonium hydroxide (26wt%) of 2mL react 10h under the conditions of 40 DEG C, separate solid product and drying, obtain
Presoma one；
Presoma one is distributed to 100mL ethyl alcohol, the mixed solution of 10mL deionized water and 5mL ammonium hydroxide (26wt%),
Under conditions of stirring, the tetraethyl orthosilicate of 5mL is added rapidly to above-mentioned solution, separates solid product and drying, obtains forerunner
Body two；
Finally under the protection of argon gas after 350 DEG C of calcining 3h, continuation calcines 3h under the conditions of 800 DEG C, after product is cooling,
It is added in the 2mol/L sodium hydroxide solution of 20ml, anti-48h, separates solid product and dry to get empty to titanium dioxide-carbon
Bulbus cordis compound；
Titanium dioxide made from 1g-carbon hollow ball compound is mixed into the 4h that mills with 4g sulphur simple substance, under the atmosphere of argon gas
155 DEG C of calcining 12h to get arrive lithium sulfur battery anode material.
The partial size of lithium sulfur battery anode material manufactured in the present embodiment is 318nm, and the internal diameter of carbon hollow ball is 280nm, outside
Diameter is 290nm, mass content 19%；The partial size of nano-titanium dioxide is 28nm, mass content 6%；The mass content of sulphur
It is 75%.
Embodiment 8:
The lithium sulfur battery anode material prepared in embodiment 7 is assembled into lithium-sulfur cell in the way of embodiment 2.
Lithium-sulfur cell manufactured in the present embodiment, at 1C, battery discharge capacity after 200 circulations still keeps 806mAh
g-1。
Embodiment 9:
It prepares mixed solution (70mL normal propyl alcohol+3mL ammonium hydroxide (26wt%)+30mL deionized water), in the item of lasting stirring
Under part, 10ml tetraethyl orthosilicate is added rapidly in above-mentioned solution, 1h is reacted at 50 DEG C, separates solid product and drying,
Both the silica that partial size is 270nm had been obtained；
The titanium dioxide that silica obtained and 2g partial size are 30nm is dispersed in 100mL deionized water and 50mL positive third
The in the mixed solvent of alcohol stirs 8min at 50 DEG C.Then the isophthalic of 1g cetyl trimethylammonium bromide, 0.54g are sequentially added
Diphenol, the formaldehyde of 1mL and the ammonium hydroxide (26wt%) of 1mL react 8h under the conditions of 50 DEG C, separate solid product and drying, obtain
Presoma one；
Presoma one is distributed to 70mL normal propyl alcohol, the mixed solution of 30mL deionized water and 4mL ammonium hydroxide (26wt%),
Under conditions of stirring, the tetraethyl orthosilicate of 5mL is added rapidly to above-mentioned solution, separates solid product and drying, obtains forerunner
Body two；
Finally under the protection of nitrogen after 350 DEG C of calcining 2h, continuation calcines 4h under the conditions of 800 DEG C, after product is cooling,
It is added in the 2mol/L sodium hydroxide solution of 20ml, reaction for 24 hours, separates solid product and drying to get titanium dioxide-carbon is arrived
Hollow sphere compound；
Titanium dioxide made from 1g-carbon hollow ball compound is mixed into the 1h that mills with 3g sulphur simple substance, under the atmosphere of argon gas
155 DEG C of calcining 10h to get arrive lithium sulfur battery anode material.
The partial size of lithium sulfur battery anode material manufactured in the present embodiment is 290nm, and the internal diameter of carbon hollow ball is 310nm, outside
Diameter is 320nm, mass content 24%；The partial size of nano-titanium dioxide is 30nm, mass content 7%；The mass content of sulphur
It is 69%.
Embodiment 10:
The lithium sulfur battery anode material prepared in embodiment 9 is assembled into lithium-sulfur cell in the way of embodiment 2.
Lithium-sulfur cell manufactured in the present embodiment, at 1C, battery discharge capacity after 200 circulations still keeps 648mAh
g-1。
As can be seen from the above embodiments, the lithium-sulfur cell of lithium sulfur battery anode material preparation provided by the invention has good
Good high rate performance and cycle performance, at 1C, discharge capacity still keeps 691mAhg after 200 circulations-1, after 300 times recycle
Discharge capacity still keeps 671mAhg-1, coulombic efficiency is maintained at 97% or so；Under 4C high rate cyclic, discharge capacity remains to protect
Hold 527mAhg-1, when turning again to 1C, discharge capacity can still keep 1042mAhg-1。
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should
It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make
Dry improvements and modifications, these modifications and embellishments should also be considered as the scope of protection of the present invention.
Claims (10)
1. a kind of lithium sulfur battery anode material, including carbon hollow ball, it is attached to the nano-silica of the carbon hollow ball surfaces externally and internally
The sulphur simple substance changing titanium and being filled in the carbon hollow ball, the mass content of the sulphur simple substance are 60~80%；
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) nanometer titanium dioxide silicon suspension is mixed with nano-titanium dioxide, obtains mixing suspension；
(2) surfactant, phenols, formaldehyde and catalyst are sequentially added in the mixing suspension that Xiang Suoshu step (1) obtains, contracted
Poly- reaction obtains the first presoma；
(3) the first presoma that the step (2) obtains is mixed with mixed solvent, tetraethyl orthosilicate, hydrolysis is added
Obtain the second presoma；
(4) it is performed etching after calcining the second presoma that the step (3) obtains, it is compound to obtain titanium dioxide-carbon hollow ball
Object；The titanium dioxide-carbon hollow ball compound includes carbon hollow ball and the nanometer for being attached to the carbon hollow ball surfaces externally and internally
Titanium dioxide；
(5) it is heat-treated, obtains after mixing titanium dioxide-carbon hollow ball compound that the step (4) obtains with sulphur simple substance
To lithium sulfur battery anode material.
2. lithium sulfur battery anode material according to claim 1, which is characterized in that the internal diameter of the carbon hollow ball is 150
~350nm, outer diameter are 200~400nm.
3. lithium sulfur battery anode material according to claim 1, which is characterized in that the grain of the lithium sulfur battery anode material
Diameter is 250~450nm.
4. the preparation method of lithium sulfur battery anode material described in claims 1 to 3 any one, comprising the following steps:
(1) nanometer titanium dioxide silicon suspension is mixed with nano-titanium dioxide, obtains mixing suspension；
(2) surfactant, phenols, formaldehyde and catalyst are sequentially added in the mixing suspension that Xiang Suoshu step (1) obtains, contracted
Poly- reaction obtains the first presoma；
(3) the first presoma that the step (2) obtains is mixed with mixed solvent, tetraethyl orthosilicate, hydrolysis is added
Obtain the second presoma；
(4) it is performed etching after calcining the second presoma that the step (3) obtains, it is compound to obtain titanium dioxide-carbon hollow ball
Object；The titanium dioxide-carbon hollow ball compound includes carbon hollow ball and the nanometer for being attached to the carbon hollow ball surfaces externally and internally
Titanium dioxide；
(5) it is heat-treated, obtains after mixing titanium dioxide-carbon hollow ball compound that the step (4) obtains with sulphur simple substance
To lithium sulfur battery anode material.
5. the preparation method according to claim 4, which is characterized in that in the step (2) temperature of polycondensation reaction be 0~
100 DEG C, the time of polycondensation reaction is 1~48h.
6. the preparation method according to claim 4, which is characterized in that the calcining in the step (4) successively includes low temperature
Calcining and high-temperature calcination, the temperature of the low temperature calcination are 200~550 DEG C.
7. preparation method according to claim 6, which is characterized in that the time of the low temperature calcination is 0.5~8h.
8. preparation method according to claim 6 or 7, which is characterized in that the temperature of the high-temperature calcination is 600~1200
DEG C, the time of high-temperature calcination is 0.5~12h.
9. the preparation method according to claim 4, which is characterized in that the temperature being heat-treated in the step (5) is 120~
180 DEG C, time of heat treatment is 3~for 24 hours.
10. a kind of lithium-sulfur cell, including anode, cathode of lithium and electrolyte, the anode includes active material, which is characterized in that
The active material is any for lithium sulfur battery anode material described in claims 1 to 3 any one or according to claim 4~9
The lithium sulfur battery anode material of one preparation method preparation.
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| CN108091839B (en) * | 2017-11-27 | 2021-03-30 | 浙江衡远新能源科技有限公司 | Preparation method of lithium-sulfur battery positive electrode slurry |
| CN109841805A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | The hollow carbon sulphur anode composite material of sheet manganese dioxide cladding and preparation and application |
| CN108899217B (en) * | 2018-07-10 | 2019-08-23 | 湖南科技大学 | A kind of carbon hollow ball that inlaying different electroactive materials, preparation method and application |
| CN108963224B (en) * | 2018-07-16 | 2020-07-07 | 杭州电子科技大学 | Preparation method of composite material for positive electrode of lithium-sulfur battery |
| CN109037657A (en) * | 2018-08-18 | 2018-12-18 | 复旦大学 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN109411719B (en) * | 2018-09-28 | 2021-11-12 | 湖北大学 | Titanium carbide/titanium dioxide-sulfur ternary composite positive electrode material, preparation method and application thereof, and lithium-sulfur battery |
| CN109216691B (en) * | 2018-11-06 | 2021-08-17 | 桑德新能源技术开发有限公司 | Positive active material, preparation method thereof and lithium battery |
| CN109698333B (en) * | 2018-12-17 | 2020-08-14 | 中国空间技术研究院 | Lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN110492071A (en) * | 2019-08-19 | 2019-11-22 | 西京学院 | Inner wall is loaded with the hollow carbon sphere and preparation method and purposes of nickel hydroxide and sulphur |
| CN110635122B (en) * | 2019-09-27 | 2021-06-25 | 清华大学深圳国际研究生院 | Ultrathin folded carbon layer coated ZnS composite interlayer material and preparation method and application thereof |
| CN111403714A (en) * | 2020-03-27 | 2020-07-10 | 清华大学深圳国际研究生院 | Lithium-sulfur battery positive electrode material, preparation method, positive plate and lithium-sulfur battery |
| CN111900351A (en) * | 2020-07-15 | 2020-11-06 | 中航锂电技术研究院有限公司 | Composite carbon material for lithium-sulfur battery, preparation method and lithium-sulfur battery |
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