CN108987729A - 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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- CN108987729A CN108987729A CN201810996798.8A CN201810996798A CN108987729A CN 108987729 A CN108987729 A CN 108987729A CN 201810996798 A CN201810996798 A CN 201810996798A CN 108987729 A CN108987729 A CN 108987729A
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Abstract
The invention discloses a kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cells.The lithium sulfur battery anode material includes several vanadium oxide nanometer sheets, several cobalt granules being dispersed in each vanadium oxide nanometer sheet, in the carbon nanotube that several cobalt granule surfaces are grown and the sulphur simple substance for being dispersed in carbon nanotube and being dispersed in the network that carbon nanotube is formed simultaneously.Lithium sulfur battery anode material provided by the invention carries out load sulphur using metallic cobalt simple substance and transition metal oxide as template growth carbon nanotube, effectively alleviate the volume expansion problem in charge and discharge process, and metallic cobalt simple substance and carbon nanotube are all good conductive materials, the shortcomings that compensating for sulphur insulating properties, the high rate performance and stable circulation performance of the lithium-sulfur cell made are greatly enhanced.And the preparation method has a simple process, easy to operate, environmental-friendly, is conducive to be mass produced, and has practicability.
Description
Technical field
The invention belongs to lithium sulfur battery anode material field, more particularly, to a kind of lithium sulfur battery anode material and its
Preparation method and lithium-sulfur cell.
Background technique
With the development of modern industry, automobile is universal, and fossil energy is caused increasingly to reduce, and environmental problem is on the rise,
Situation allows of no optimist.It is badly in need of studying clean, the reproducible energy to replace existing non-renewable fossil energy, it is same with this
When, the solution of energy storage problem is just brought into schedule.Currently, Study on Li-ion batteries, using relatively broad, because its power density,
The advantages that energy density is relatively high, has extended cycle life, environmentally protective makes it in all kinds of mobile power sources, large-scale energy storage device and
It is widely applied on New-energy electric vehicle.However, the lithium ion positive and negative pole material nowadays studied, capacity nearly reach its reason
By capacity, it is difficult to meet growing energy storage demand.Therefore, it is badly in need of developing the electrode material with higher energy density
To push the further development of society.At this point, lithium-sulfur cell is gradually climbed up with the theoretical specific capacity of its high specific energy and material
The stage of energy storage.
Lithium-sulfur cell is a kind of lithium battery of the lithium metal as negative electrode material using element sulphur as cell positive material.Its
In, elemental sulfur is quite abundant in the reserves of the earth, cheap advantage, and element sulphur no pollution to the environment are made it have,
Belong to clean energy and material.Secondly, sulphur, as positive electrode, theoretical specific capacity may be up to 1675mA/g, the theory of battery
Specific energy is up to 2600Wh/kg, and considerably beyond the cobalt acid lithium battery capacity (150mAh/g) on existing market, this just makes lithium sulphur electric
Pond becomes energy storage mode very with application prospect.But there is also its peculiar problems for lithium-sulfur cell: (1) conduction of sulphur
Property it is excessively poor, and react final product Li2S2And Li2S is insulator, causes battery high rate performance poor；(2) lithium sulphur
The intermediate product polysulfide of battery can be dissolved into electrolyte, reduce ionic conductivity, and polysulfide is in positive and negative anodes
Between movement, lose active material, so that cyclical stability be made to reduce；(3) in charge and discharge process, sulphur volume can become larger,
It is easily damaged battery and brings security risk.
To solve the problems, such as that lithium-sulfur cell is existing, positive electrode need to be modified to realize.Present most of researchs
Technology is mainly, and sulphur and single conductive base material or metal oxide materials are carried out compound to improve performance.But it is above-mentioned
It is limited for the inhibiting effect of the raising of material conductivity and polysulfide shuttle effect in method, to improving lithium-sulfur cell simultaneously
High rate performance and cycle performance ability it is also limited.
Summary of the invention
A kind of lithium sulfur battery anode material and preparation method thereof and lithium are provided for the technical problems in the prior art
Sulphur battery.The lithium sulfur battery anode material is capable of providing high electric conductivity, catalytic performance and chemically inhibits polysulfide
Shuttle effect, to improve the high rate performance and cycle performance of lithium-sulfur cell.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of lithium sulfur battery anode material, the lithium sulfur battery anode material include several vanadium oxide nanometer sheets, are dispersed in
Several cobalt granules in each vanadium oxide nanometer sheet, the growth of several cobalt granule surfaces carbon nanotube and be dispersed in carbon nanometer
The sulphur simple substance being dispersed in the network of carbon nanotube formation in pipe and simultaneously.
In above scheme, the vanadium oxide nanometer sheet is hexagon.
In above scheme, the side length of the vanadium oxide nanometer sheet is 2-3 μm, 1-1.5 μm thick.
In above scheme, the diameter of the cobalt granule and carbon nanotube is 10-30nm.
The preparation method of the lithium sulfur battery anode material, comprising the following steps:
(1) urotropine, cobalt chloride hexahydrate, ammonium metavanadate presoma are added to the water mixing, are mixed
Object；
(2) mixture prepared by step (1) is put into water-bath, stirred to get vanadic acid cobalt powder powder material；
(3) vanadic acid cobalt material described in step (2) is placed in tube furnace, under carbon monoxide atmosphere, heat treatment is carried out
Mutually separation and synchronous growth carbon nanotube clad.
(4) vacuum and low temperature heat treatment is carried out after mixing composite material described in step (3) with sublimed sulfur to get described in
Lithium sulfur battery anode material.
In above scheme, the mass ratio of urotropine, cobalt chloride hexahydrate and ammonium metavanadate is 1 in step (1):
4~5:12~13.
In above scheme, step (2) water bath temperature is 80 DEG C, and soaking time is 4h.
In above scheme, step (3) heat treatment temperature be 580 DEG C -620 DEG C, heating rate be 5 DEG C/min-10 DEG C/
Min, soaking time 1-3h.
In above scheme, the heat treatment temperature of step (4) is 150 DEG C -160 DEG C, heating rate is 1 DEG C/min-10 DEG C/
Min, soaking time 10-13h.
A kind of lithium-sulfur cell, including anode, cathode of lithium and electrolyte, the anode include active material, the active matter
Matter is the lithium sulfur battery anode material or the lithium sulfur battery anode material being prepared according to the preparation method.
Compared with prior art, the present invention has the beneficial effects that
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 vanadium oxide piece, wraps the carbon nano tube network for investing piece surface and metallic cobalt simple substance and is filled in network
In sulphur simple substance.Lithium sulfur battery anode material provided by the invention is using metallic cobalt simple substance and transition metal oxide as template growth
Carbon nanotube carries out load sulphur, effectively alleviates the volume expansion problem in charge and discharge process, and metallic cobalt simple substance and carbon are received
The shortcomings that mitron is all good conductive material, compensates for sulphur insulating properties；Secondly, metallic cobalt simple substance has catalytic action, promote
The progress of reaction；Vanadium oxide has chemisorption to sulphur and polysulfide, can effectively inhibit polysulfide and react
Shuttle effect in the process；In addition, vanadium oxide piece and the carbon nano tube network of periphery add cobalt simple substance, sulphur appropriate is cooperated to contain
Amount, enables this composite construction to promote electron-transport simultaneously, and lithium ion can be made quickly to be transferred on the sulphur of low conduction, thus
To improve the high rate performance and stable circulation performance of lithium-sulfur cell.Originally the experimental results showed that, lithium-sulfur cell provided by the invention is just
The lithium-sulfur cell of pole material preparation is at 1C, and after 200 circulations, discharge capacity is still able to maintain 501mAh/g, puts after 300 circulations
Capacitance can keep 451mAh/g, and coulombic efficiency remains at 100% or so；Under 5C high rate cyclic, discharge capacity remains to protect
532mAh/g is held, when turning again to 1C, discharge capacity can still keep 679mAh/g.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of lithium sulfur battery anode material prepared by the embodiment of the present invention 1；
Fig. 2 is that the metal simple-substance that the embodiment of the present invention 1 is prepared and vanadium oxide nanometer sheet grow carbon nano-tube material
Scanning electron microscope (SEM) photograph；
Fig. 3 is that the metal simple-substance that the embodiment of the present invention 1 is prepared and vanadium oxide nanometer sheet grow carbon nano-tube material and inhale
The adsorption effect figure of attached polysulfide；
Fig. 4 is the charging and discharging curve that lithium-sulfur cell is prepared in the embodiment of the present invention 1；
Fig. 5 is the high rate performance figure that lithium-sulfur cell is prepared in the embodiment of the present invention 1；
Fig. 6 is the cycle performance figure that lithium-sulfur cell is prepared in the embodiment of the present invention 1.
Specific embodiment
Those skilled in the art are made to better understand technical solution of the present invention, it is right in the following with reference to the drawings and specific embodiments
The present invention elaborates.
As shown in Figure 1, it is a kind of lithium sulfur battery anode material provided by the invention, including several vanadium oxide nanometer sheets,
Several cobalt granules for being dispersed in each vanadium oxide nanometer sheet, the growth of several cobalt granule surfaces carbon nanotube and be dispersed in
The sulphur simple substance being dispersed in the network of carbon nanotube formation in carbon nanotube and simultaneously.
In the present invention, the vanadium oxide nanometer sheet is hexagon, 1-1.5 μm thick its side length is 2-4 μm.The present invention couple
The content of the vanadium oxide piece is not particularly limited.In the present invention, the vanadium oxide piece has stable shape.In the present invention
In, the vanadium oxide piece has chemisorption to sulphur and polysulfide, can effectively inhibit the shuttle effect of polysulfide.
Lithium sulfur battery anode material provided by the invention further includes the nano cobalt granule for interspersing among vanadium nitride on piece.In this hair
In bright, the partial size of the nano cobalt granule is preferably 10-30nm.The present invention is to the nano cobalt granule in vanadium oxide piece outer surface
Distribution density be not particularly limited, the content distribution according to vanadium oxide and cobalt nano-particle is uniform.In the present invention, institute
Metal simple-substance nano cobalt granule is stated with high conductivity, guarantees the high usage and excellent high rate performance of sulphur.In the present invention
In, the metal simple-substance nano cobalt granule has catalytic action to the discharge and recharge reaction of battery, promotes going on smoothly for reaction.
Lithium sulfur battery anode material provided by the invention further includes the carbon nano tube network being coated on the outside of vanadium oxide.At this
In invention, the carbon nano tube network provides bigger storage space for elemental sulfur, improves the carrying capacity of elemental sulfur and can delay
Solve volume change of the sulphur in charge and discharge process.In the present invention, the carbon nanotube diameter 10-30nm.In the present invention, institute
Stating length of carbon nanotube is 1-3 μm.In the present invention, the carbon nanotube has excellent electric conductivity, makes up elemental sulfur and anti-
It answers product lithium sulfide or vulcanizes the insulating properties of two lithiums.
Lithium sulfur battery anode material provided by the invention includes being filled in inside carbon nano tube network and in carbon nanotube
Sulphur simple substance.The present invention is not particularly limited compactedness of the sulphur simple substance in carbon nano tube network, can be according to sulphur simple substance
Content is adjusted.In the present invention, active material of the sulphur simple substance of the certain content as positive electrode is aoxidized in sheet
Under the collective effect of vanadium, metal simple-substance nano cobalt granule and carbon nano tube network, this composite material is made to can guarantee electronics and ion
Quick transmission and mobile, reach the cycle performance and high rate performance for improving lithium-sulfur cell.
The present invention provides the preparation methods of lithium sulfur battery anode material described in above-mentioned technical proposal, comprising the following steps:
1) urotropine, cobalt chloride hexahydrate, ammonium metavanadate presoma are added in pure water and are mixed, mixed
Object；
(2) mixture prepared by step (1) is put into water-bath, stirred to get vanadic acid cobalt powder powder material；
(3) vanadic acid cobalt material described in step (2) is placed in tube furnace, under carbon monoxide atmosphere, heat treatment is carried out
Mutually separation and synchronous growth carbon nanotube clad.
(4) vacuum and low temperature heat treatment is carried out after mixing composite material described in step (3) with sublimed sulfur to get described in
Lithium sulfur battery anode material.
The preparation principle of lithium sulfur battery anode material of the present invention is to synthesize vanadic acid cobalt by predecessor stirring in water bath, in an oxidation
After handling in carbon atmosphere, vanadic acid cobalt isolates vanadium oxide and metallic cobalt, and under the catalytic action of metallic cobalt, carbon monoxide is provided
Carbon source, and grown carbon nanotube in Metallic cobalt surface, finally through Overheating Treatment, sulphur simple substance is packed into carbon nano tube network
In, obtain lithium sulfur battery anode material.
Urotropine, cobalt chloride hexahydrate, ammonium metavanadate presoma are added in pure water and are mixed by the present invention, are obtained
Mixture.In the present invention, the urotropine, cobalt chloride hexahydrate, ammonium metavanadate mass ratio be 1:4~5:12
~13.In water-bath, temperature setting is 80 DEG C, after stirring 4h, obtains vanadic acid cobalt product.Then by it in an oxygen
Change in carbon atmosphere, treatment temperature is 580 DEG C -620 DEG C, and time 1-3h, heating rate is set as 5 DEG C/min-10 DEG C/min, just
Metal-oxide Surface Creation carbon nano tube network can be obtained, by being 150 DEG C -160 DEG C in temperature, steam sulphuring treatment 10-13h
Afterwards, it can obtain as load sulphur medium and be applied to lithium sulfur battery anode material.In invention, the heat treatment fills elemental sulfur
It is limited to alleviate sulphur volume change in charge and discharge process in carbon nano tube network.
The not special restriction of the operation that the present invention mixes three kinds of predecessors, using water familiar to those skilled in the art
Bath method.In the present invention, the urotropine, cobalt chloride hexahydrate, the water-bath of ammonium metavanadate mixture are anti-
Answering temperature is preferably 80 DEG C.The water of the urotropine, cobalt chloride hexahydrate, ammonium metavanadate mixture in the present invention
Bath reaction is preferably keeping stirring lower progress；The stirring is preferably magnetic agitation；The rate of the stirring is preferably 300-
600r/min, more preferably 400-500r/min；The time of the stirring is preferably 3-6h, more preferably 4-5h.
The present invention is not particularly limited the operation of the preparation of the vanadic acid cobalt, and use is well known to those skilled in the art
The technical solution of water-bath.The preparation of the vanadic acid cobalt preferably includes following steps: by urotropine, six water
Cobalt chloride, ammonium metavanadate and pure water mixing are closed, mixed solvent is obtained.
After water-bath, the currently preferred product by above-mentioned water-bath is separated by solid-liquid separation, and then will be separated
The solid arrived is dry, obtains vanadic acid cobalt material.The present invention is not particularly limited the separation of solid and liquid and dry operation, uses
Separation of solid and liquid well known to those skilled in the art and dry technical solution.In the present invention, described to be separated by solid-liquid separation preferably
To filter, the suction filtration number is preferably 2 times.
After obtaining vanadic acid cobalt material, the vanadic acid cobalt material is heat-treated by the present invention, obtains metal simple-substance cobalt granule
With sheet vanadium oxide enveloped carbon nanometer tube network.In the present invention, the heat treatment temperature is preferably 580 DEG C -620 DEG C, preferably
It is 590 DEG C -610 DEG C；The heat treatment temperature is 1-3h, preferably 2.5h-1.5h.In the present invention, the heat treatment is preferred
It is carried out under carbon monoxide atmosphere.Heat treatment heating rate of the present invention is preferably 5 DEG C/min-10 DEG C/min.
Obtain being distributed with metal simple-substance cobalt granule on sheet vanadium oxide and after periphery is coated with the material of carbon nano tube network,
The present invention is heat-treated after mixing above-mentioned composite material with sulphur simple substance, obtains lithium sulfur battery anode material.
The no particular provisions of the operation that the present invention mixes above-mentioned composite material with elemental sulfur, using those skilled in the art
The technical solution of well known powder mixing.In the present invention, above-mentioned composite material is mixed preferably to grind with elemental sulfur and be mixed
It closes, the ground and mixed time is preferably 0.5-3h, preferably 1-2h.The temperature being heat-treated after mixing is preferably 150 DEG C-
165 DEG C, most preferably 155 DEG C -160 DEG C；The heat treatment time is preferably 10-13h, most preferably 11-12h.In the present invention,
The heat treatment is filled in elemental sulfur in carbon nano tube network, limited to alleviate sulphur volume change in charge and discharge process.
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.
Illustrated below with several specific embodiments.
Embodiment 1
The present embodiment provides the preparation methods of the lithium sulfur battery anode material, comprising the following steps:
(1) urotropine, cobalt chloride hexahydrate, ammonium metavanadate presoma are mixed by 1:5:12.5, is mixed
Close object；
(2) container equipped with reactant is put into 80 DEG C of water-baths, keeps stirring 4h to get vanadic acid cobalt material；
(3) resulting vanadic acid cobalt will be reacted to filter 2 times, remove the complete predecessor of unreacted；
(4) final resulting vanadic acid cobalt material is placed in tube furnace, is heat-treated under carbon monoxide atmosphere, with 5 DEG C/
The heating rate of min is heated to 600 DEG C, and soaking time is that 2h carries out mutually separation and synchronous growth carbon nano tube network clad,
It is taken out after product cools to room temperature with the furnace.
(5) 155 DEG C of Low Temperature Heat Treatment 12h are carried out after being sufficiently mixed after mixing above-mentioned composite material with sublimed sulfur, i.e.,
Obtain the lithium sulfur battery anode material.
The flow chart prepared in Fig. 1 for the embodiment of the present invention 1；It can by the scanning electron microscope (SEM) photograph of Fig. 2 (including Fig. 2A, Fig. 2 B)
Know, the final product that the present embodiment is prepared is the carbon nano-tube network of vanadium oxide piece and outer layer by metal simple substance cobalt catalytic growth
Network structure.It follows that products therefrom is with high electric conductivity, catalytic, adsorptivity and biggish load sulphur gap.Fig. 3 is
The charging and discharging curve of institute's lithium-sulfur cell, Fig. 4 are the high rate performance figure of lithium-sulfur cell, and Fig. 5 is the cycle performance figure of lithium-sulfur cell,
Under 1C, after 200 circulations, discharge capacity is still able to maintain 501mAh/g, and discharge capacity can keep 451mAh/g after 300 circulations,
Coulombic efficiency remains at 98% or so；Under 5C high rate cyclic, discharge capacity is still able to maintain 532mAh/g, turns again to 1C
When, discharge capacity can still keep 679mAh/g.
Embodiment 2
The present embodiment provides the preparation methods of the lithium sulfur battery anode material, comprising the following steps:
(1) urotropine, cobalt chloride hexahydrate, ammonium metavanadate presoma are mixed by 1:5:12.5, is mixed
Close object；
(2) container equipped with reactant is put into 80 DEG C of water-baths, keeps stirring 4h to get vanadic acid cobalt material；
(3) resulting vanadic acid cobalt will be reacted to filter 2 times, remove the complete predecessor of unreacted；
(4) final resulting vanadic acid cobalt material is placed in tube furnace, is heat-treated under carbon monoxide atmosphere, with 5 DEG C/
The heating rate of min is heated to 580 DEG C, and soaking time is that 3h carries out mutually separation and synchronous growth carbon nanotube clad, wait produce
Object takes out after cooling to room temperature with the furnace.
(5) 160 DEG C of Low Temperature Heat Treatments are carried out after being sufficiently mixed after mixing above-mentioned composite material with sublimed sulfur to get arriving
The lithium sulfur battery anode material.At 1C, after 200 circulations, discharge capacity is still able to maintain 497mAh/g, 300 circulations
Discharge capacity can keep 445mAh/g afterwards, and coulombic efficiency remains at 98% or more；Under 5C high rate cyclic, discharge capacity is remained to
526mAh/g is kept, when turning again to 1C, discharge capacity can still keep 661mAh/g.
Embodiment 3
The present embodiment provides the preparation methods of the lithium sulfur battery anode material, comprising the following steps:
(1) urotropine, cobalt chloride hexahydrate, ammonium metavanadate presoma are mixed by 1:5:12.5, is mixed
Close object；
(2) container equipped with reactant is put into 80 DEG C of water-baths, keeps stirring 4h to get vanadic acid cobalt material；
(3) resulting vanadic acid cobalt will be reacted to filter 2 times, remove the complete predecessor of unreacted；
(3) final resulting vanadic acid cobalt material is placed in tube furnace, is heat-treated under carbon monoxide atmosphere, with 5 DEG C/
The heating rate of min is heated to 620 DEG C, and soaking time is that 2h carries out mutually separation and synchronous growth carbon nanotube clad, wait produce
Object takes out after cooling to room temperature with the furnace.
(4) 155 DEG C of Low Temperature Heat Treatments are carried out after being sufficiently mixed after mixing above-mentioned composite material with sublimed sulfur to get arriving
The lithium sulfur battery anode material.At 1C, after 200 circulations, discharge capacity is still able to maintain 491mAh/g, 300 circulations
Discharge capacity can keep 442mAh/g afterwards, and coulombic efficiency remains at 98% or more；Under 5C high rate cyclic, discharge capacity is remained to
528mAh/g is kept, when turning again to 1C, discharge capacity can still keep 670mAh/g.
Above embodiments are only exemplary embodiment of the present invention, are not used in the limitation present invention, protection scope of the present invention
It is defined by the claims.Those skilled in the art can within the spirit and scope of the present invention make respectively the present invention
Kind modification or equivalent replacement, this modification or equivalent replacement also should be regarded as being within the scope of the present invention.
Claims (10)
1. a kind of lithium sulfur battery anode material, which is characterized in that the lithium sulfur battery anode material includes several vanadium oxide nanometers
Piece, several cobalt granules being dispersed in each vanadium oxide nanometer sheet, carbon nanotube and dispersion in the growth of several cobalt granule surfaces
The sulphur simple substance being dispersed in the network of carbon nanotube formation in carbon nanotube and simultaneously.
2. lithium sulfur battery anode material as described in claim 1, which is characterized in that the vanadium oxide nanometer sheet is hexagon.
3. lithium sulfur battery anode material as claimed in claim 2, which is characterized in that the side length of the vanadium oxide nanometer sheet is 2-
It is 4 μm, 1-1.5 μm thick.
4. lithium sulfur battery anode material as described in claim 1, which is characterized in that the diameter of the cobalt granule and carbon nanotube
It is 10-30nm.
5. as the described in any item lithium sulfur battery anode materials of Claims 1-4 preparation method, which is characterized in that including with
Lower step:
(1) urotropine, cobalt chloride hexahydrate, ammonium metavanadate presoma are added to the water mixing, obtain mixture；
(2) mixture prepared by step (1) is put into water-bath, stirred to get vanadic acid cobalt powder powder material；
(3) vanadic acid cobalt material described in step (2) is placed in tube furnace, under carbon monoxide atmosphere, heat treatment carries out phase point
From with synchronous growth carbon nanotube clad；
(4) vacuum and low temperature heat treatment is carried out after mixing composite material described in step (3) with sublimed sulfur to get the lithium is arrived
Sulphur cell positive electrode material.
6. preparation method as claimed in claim 5, which is characterized in that urotropine, six chloride hydrates in step (1)
The mass ratio of cobalt and ammonium metavanadate is 1:4~5:12~13.
7. preparation method as claimed in claim 5, which is characterized in that step (2) water bath temperature is 80 DEG C, and is kept the temperature
Time is 4h.
8. preparation method as claimed in claim 5, which is characterized in that step (3) heat treatment temperature is 580 DEG C -620
DEG C, heating rate is 5 DEG C/min-10 DEG C/min, soaking time 1-3h.
9. preparation method as claimed in claim 5, which is characterized in that the heat treatment temperature of step (4) is 150 DEG C -165 DEG C,
Heating rate is 1 DEG C/min-10 DEG C/min, soaking time 10-13h.
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 for the described in any item lithium sulfur battery anode materials of claim 1-4 or according to any one of claim 5-8
The lithium sulfur battery anode material that the preparation method is prepared.
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| CN110380052A (en) * | 2019-07-19 | 2019-10-25 | 田韬 | One kind being based on the highly conductive sulfenyl composite material of lithium-sulphur cell positive electrode |
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| CN115083799A (en) * | 2022-06-30 | 2022-09-20 | 江苏大学 | Macroporous self-supporting CNTs @ Co 2 V 2 O 7 Preparation method and application of composite film with black phosphorus quantum dots loaded thereon |
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| CN109888176A (en) * | 2019-01-22 | 2019-06-14 | 浙江工业大学 | A kind of anode of lithium-sulfur rechargeable battery |
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| CN115036480A (en) * | 2022-06-17 | 2022-09-09 | 湘潭大学 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
| CN115083799A (en) * | 2022-06-30 | 2022-09-20 | 江苏大学 | Macroporous self-supporting CNTs @ Co 2 V 2 O 7 Preparation method and application of composite film with black phosphorus quantum dots loaded thereon |
| CN115083799B (en) * | 2022-06-30 | 2023-05-09 | 江苏大学 | Macroporous self-supporting CNTs@Co 2 V 2 O 7 Preparation method and application of composite film with black phosphorus quantum dots loaded thereon |
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