CN108987714A - Lithium-sulphur cell positive electrode active material and preparation method thereof, lithium sulfur battery anode material and lithium-sulfur cell - Google Patents
Lithium-sulphur cell positive electrode active material and preparation method thereof, lithium sulfur battery anode material and lithium-sulfur cell Download PDFInfo
- Publication number
- CN108987714A CN108987714A CN201810805508.7A CN201810805508A CN108987714A CN 108987714 A CN108987714 A CN 108987714A CN 201810805508 A CN201810805508 A CN 201810805508A CN 108987714 A CN108987714 A CN 108987714A
- Authority
- CN
- China
- Prior art keywords
- lithium
- positive electrode
- electrode active
- sulphur
- active material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of lithium-sulphur cell positive electrode active material and preparation method thereof, lithium sulfur battery anode material and lithium-sulfur cells.It is related to battery material technical field, the positive electrode active materials include the lithium sulfide of sintering connection and the carbon material doped with element sulphur, are alleviated existing using Li2S/ metal oxide or Li2When S/ carbon composite is as lithium-sulphur cell positive electrode active material, the technical problem of lithium-sulfur cell cyclical stability difference.The present invention passes through lithium sulfide is mutually compound doped with the carbon material of element sulphur, the electric conductivity of lithium sulfide can be significantly improved, simultaneously doped with the carbon material of element sulphur, binding site can be provided for polysulfide, improve the binding force of polysulfide and positive electrode active materials, so that lithium-sulfur cell is able to maintain higher specific capacity, cyclical stability is significantly improved.
Description
Technical field
The present invention relates to battery material technical fields, more particularly, to a kind of lithium-sulphur cell positive electrode active material and its preparation
Method, lithium sulfur battery anode material and lithium-sulfur cell.
Background technique
Lithium-sulfur cell is using sulphur as positive active material, and lithium metal is cathode, the battery being composed.Sulphur is as a kind ofly
The relatively high element of abundance on ball, have it is at low cost, the high feature of energy density, theoretical energy density reaches 1675mAh/g, sulphur
After electric discharge completely, Li is ultimately generated2S.In recent years, with Li2S is that lithium-sulphur cell positive electrode active material is widely studied, theoretical
Capacity reaches 1166mAh/g.But Li2The same conductive energy of S is poor, and more lithium sulfides are generated in charge and discharge process and are easy to molten
Solution in the electrolytic solution, the disadvantages of leading to the poor circulation of lithium-sulfur cell.
Li is used in the prior art2S/ metal oxide, Li2Positive-active material of the S/ carbon composite as lithium-sulfur cell
Material has certain improvement to the comprehensive performance of lithium-sulfur cell, but its there are still the more sulphur generated with lithium sulfide and in charge and discharge process
Change the weaker disadvantage of the binding force of lithium, limits the raising of the cycle performance of lithium-sulfur cell.
In view of this, the present invention is specifically proposed.
Summary of the invention
It is existing to alleviate one of the objects of the present invention is to provide a kind of preparation method of lithium-sulphur cell positive electrode active material
Using Li2S/ metal oxide or Li2When S/ carbon composite is as lithium-sulphur cell positive electrode active material, lithium-sulfur cell circulation is steady
The technical problem of qualitative difference.
Lithium-sulphur cell positive electrode active material provided by the invention, including being sintered the lithium sulfide of connection and doped with element sulphur
Carbon material.
Further, the lithium-sulphur cell positive electrode active material further includes conductive materials, the conductive materials, the vulcanization
Lithium and the carbon material doped with element sulphur are sintered connection.
The second object of the present invention is that the preparation method for providing a kind of lithium-sulphur cell positive electrode active material includes following step
It is rapid:
After mixing by lithium sulfide and sulfurous organic compound, or by sulfide, sulfurous organic compound and conductive materials it mixes equal
After even, roasted to get lithium-sulphur cell positive electrode active material is arrived；Wherein,
In the lithium-sulphur cell positive electrode active material, lithium sulfide and the carbon material doped with element sulphur are sintered connection；Or
Lithium sulfide and doped with element sulphur carbon material and conductive materials be sintered connection.
Further, first lithium sulfide and sulfurous organic compound are dissolved separately in after removing solvent after mixing in solvent,
Or first lithium sulfide, sulfurous organic compound and conductive materials are dissolved separately in solvent and remove solvent after mixing, obtain forerunner
Body material；
Persursor material is roasted again, obtains lithium-sulphur cell positive electrode active material.
Further, the sulfurous organic compound is the polymer containing carbon and element sulphur；
Preferably, the polymer containing carbon and element sulphur is the polymerization containing carbon and element sulphur on main chain
Object；
Preferably, the polymer containing carbon and element sulphur in polythiophene, polysulfones or polythiaether at least
It is a kind of.
Further, the conductive materials are selected from carbon nanotube, carbon fiber, graphene, graphene oxide or conductive black
At least one of.
Further, it is roasted under inert gas protection；
Preferably, when roasting, heating rate is 1-5 DEG C/min, rises to 600-1000 DEG C, keeps the temperature 0.5-3h to get lithium is arrived
Sulphur cell positive electrode active material.
Further, the solvent is selected from N-Methyl pyrrolidone, tetrahydrofuran, chloroform, toluene, dimethylbenzene, dichloro-benzenes
Or at least one of dimethyl sulfoxide.
The second object of the present invention is to provide a kind of lithium sulphur positive electrode, including lithium-sulphur cell positive electrode provided by the invention
The positive electrode active materials that the preparation method of active material or the lithium-sulphur cell positive electrode active material provided according to the present invention obtains.
The third object of the present invention is to provide a kind of lithium-sulfur cell, including lithium-sulphur cell positive electrode provided by the invention activity
Material, the obtained positive electrode active materials of preparation method of lithium-sulphur cell positive electrode active material provided by the invention or the present invention provide
Lithium sulfur battery anode material.
Lithium-sulphur cell positive electrode active material provided by the invention by lithium sulfide with doped with the carbon material phase of element sulphur
It is compound, the electric conductivity of lithium sulfide can be significantly improved, while doped with the carbon material of element sulphur, knot can be provided for polysulfide
Coincidence point improves the binding force of polysulfide and positive electrode active materials, so that lithium-sulfur cell is able to maintain higher specific volume
Amount, cyclical stability significantly improve.
The preparation method of lithium-sulphur cell positive electrode active material provided by the invention is by mixing lithium sulfide and sulfurous organic compound
It is roasted after conjunction, obtains lithium sulfide and the lithium-sulphur cell positive electrode active material compound doped with the carbon material of element sulphur, technique letter
It is single, it is easy to operate, it is suitable for industrialized production, reduces production cost, improves production efficiency.
Lithium sulfur battery anode material provided by the invention uses lithium-sulphur cell positive electrode active material conduct provided by the invention
Positive electrode active materials improve the electric conductivity of positive electrode, so that lithium-sulfur cell is able to maintain higher specific capacity, follow
Ring stability significantly improves.
Lithium-sulfur cell provided by the invention is using lithium-sulphur cell positive electrode active material provided by the invention as positive-active
Material can not only keep higher specific capacity, and cyclical stability significantly improves.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
The one aspect provided according to the present invention, the present invention provides a kind of lithium-sulphur cell positive electrode active materials, including sulphur
Change lithium and the carbon material doped with element sulphur, the two sintering connection.
Lithium-sulphur cell positive electrode active material provided by the invention by lithium sulfide with doped with the carbon material phase of element sulphur
It is compound, the electric conductivity of lithium sulfide can be significantly improved, while doped with the carbon material of element sulphur, knot can be provided for polysulfide
Coincidence point improves the binding force of polysulfide and positive electrode active materials, so that lithium-sulfur cell is able to maintain higher specific volume
Amount, cyclical stability significantly improve.
In the preferred embodiment of the present invention, lithium-sulphur cell positive electrode active material further includes conductive materials, conductive
Substance, lithium sulfide and the carbon material doped with element sulphur are sintered connection.
By the way that conductive materials are added in lithium-sulphur cell positive electrode active material, so that lithium sulfide and conductive materials and doping
It is mutually cooperateed with by the carbon material of element sulphur, significantly improves the electric conductivity of positive electrode active materials.
According to the second aspect of the invention, the present invention provides a kind of preparation method of lithium sulfur battery anode material, packets
It includes following steps: lithium sulfide, the polymer containing carbon and element sulphur and optional conductive materials being uniformly mixed, are roasted
It burns, obtains sulphur lithium-sulphur cell positive electrode active material；Wherein,
In lithium-sulphur cell positive electrode active material, lithium sulfide and carbon material and optional conductive materials burning doped with element sulphur
Knot connection.
In the present invention, wherein lithium sulfide: polymer: the mass ratio of conductive agent is 100:10~100:0.5~10；
Further preferred 100:20~80:3~7；Further preferably: 100:30~60:4~6；Still more preferably 100:40~
50:5~6.
The preparation method of lithium-sulphur cell positive electrode active material provided by the invention passes through will be by lithium sulfide and sulfurous organic compound
After mixing, or by sulfide, sulfurous organic compound and conductive materials after mixing, roasted, obtain compound lithium sulphur
Battery anode active material, simple process is easy to operate, is suitable for industrialized production, reduces production cost, improves production effect
Rate.
In the preferred embodiment of the present invention, in the preparation of lithium-sulphur cell positive electrode active material provided by the invention
In method, first by lithium sulfide and sulfurous organic compound be dissolved separately in solvent be uniformly mixed removal solvent after, or first by lithium sulfide,
Sulfurous organic compound and conductive materials are dissolved separately in solvent removes solvent after mixing, obtains persursor material；It removes molten
Agent obtains persursor material, then persursor material is roasted, and obtains lithium-sulphur cell positive electrode active material.
By being dissolved in solvent by lithium sulfide and sulfurous organic compound, or by lithium sulfide and sulfurous organic compound and conductive materials
In, it is subsequent to remove solvent again, the more uniform of above-mentioned substance mixing can be conducive to generate in roasting process more stable
Lithium-sulphur cell positive electrode active material.
In the preferred embodiment of the present invention, the sulfurous organic compound is the polymerization containing carbon and element sulphur
Object.
By selecting carbon source of the polymer for containing carbon and element sulphur as sulfur-bearing, can be mixed with lithium sulfide
It is more uniform.
In present invention further optimization embodiment, the polymer containing carbon and element sulphur is to contain on main chain
The polymer of carbon and element sulphur.
By selecting the polymer containing carbon and element sulphur on main chain, makes it during roasting, be capable of forming
Element sulphur equally distributed sulfur doping carbon material in carbon material.
In present invention further optimization embodiment, the polymer containing carbon and element sulphur be selected from polythiophene,
One or more of polysulfones or polythiaether.
In the preferred embodiment of the present invention, the Weight-average molecular of the polymer containing carbon and element sulphur
Amount is 103-106, to guarantee that polymer can be completely dissolved in a solvent, achieve the effect that evenly dispersed.
In the preferred embodiment of the present invention, conductive materials are selected from carbon nanotube, graphene and graphene oxide
Or one or more of conductive carbon black.
By being sintered again after selecting conductive materials and sulfurous organic compound and lithium sulfide to be blended, so that the anode generated is living
In property substance, conductive materials are mutually cooperateed with doped with the carbon material and lithium sulfide of element sulphur, significantly improve positive electrode active materials
Electric conductivity.
In the preferred embodiment of the invention, by the way that conductive materials are mixed progress with lithium sulfide and sulfurous organic compound
Roasting not only increases just so that conductive materials after roasting, combining closely doped with the carbon material of element sulphur and lithium sulfide three
The electric conductivity of pole active material, and improve the stability of positive electrode active materials.
In the preferred embodiment of the present invention, it is roasted under inert gas protection.
By being roasted under inert gas protection, to avoid other impurity elements are introduced in roasting process, influence
The performance of positive electrode active materials.
In the preferred embodiment of the invention, inert gas is selected from least one of helium, nitrogen and argon gas, excellent
It is selected as argon gas.
In the preferred embodiment of the present invention, in roasting, heating rate is 1-5 DEG C/min, rises to 600-
1000 DEG C, 0.5-3h is kept the temperature to get lithium-sulphur cell positive electrode active material is arrived.
In the preferred embodiment of the invention, when being roasted, typical but non-limiting heating rate for example 1,
1.5,2,2.5,3,3.5,4,4.5 or 5 DEG C/min, typical but non-limiting holding temperature for example 600,650,700,750,
800,850,900,950 or 1000 DEG C, for example 0.5,0.8,1,1.5,2,2.5 or 3h of typical but non-limiting soaking time.
When by control roasting, heating rate is 1-5 DEG C/min, rises to 600-1000 DEG C, 0.5-3h is kept the temperature, so that sulphur
Change lithium, doped with element sulphur carbon material and conductive materials combine more uniform densification, with guarantee made of lithium-sulfur cell just
The stability of pole active material.
In present invention further optimization embodiment, when roasting, heating rate is 2 DEG C/min, and holding temperature is
800-900 DEG C, when soaking time is 1-2h, roasting effect is more preferably.
In the preferred embodiment of the present invention, the solution for mixing three kinds of raw materials is selected from N-Methyl pyrrolidone, four
One or more of hydrogen furans, chloroform, toluene, dimethylbenzene, dichloro-benzenes or dimethyl sulfoxide.
By selecting organic solvent to be used as the solvent for being that raw material so that three kinds of raw materials mix it is more uniform, just
The more stable lithium-sulphur cell positive electrode active material of performance is made in roasting process in subsequent.
In the preferred embodiment of the present invention, the method for solvent removal is selected from rotary evaporation, heating evaporation or cold
One of dry, preferably rotary evaporation is lyophilized.
When selecting rotary evaporation removal solvent, on the one hand it can on the other hand be conducive to lithium sulfide with recycling design and lead
Isoelectric substance is uniformly dispersed；When selecting freeze-drying, then the uniformity of material mixing is able to maintain.
According to the third aspect of the present invention, the present invention provides a kind of lithium sulfur battery anode materials, including the present invention to mention
The positive electrode active materials that the lithium-sulfur cell active material of confession or the preparation method provided according to the present invention obtain.
In the preferred embodiment of the present invention, lithium sulfur battery anode material further includes conductive agent and adhesive.
In the preferred embodiment of the present invention, conductive agent is selected from graphite, carbon black, acetylene black, graphene, carbon fiber
With one or more in carbon nanotube.
In the preferred embodiment of the present invention, adhesive is selected from polyacrylic acid, polytetrafluoroethylene (PTFE), gathers inclined chloroethene
Alkene, soluble poly tetrafluoroethene, butadiene-styrene rubber, hydroxypropyl methyl cellulose, methylcellulose, carboxymethyl cellulose, polyethylene
One or more of alcohol, acrylonitrile copolymer, sodium alginate, chitosan and chitosan derivatives.
Lithium sulfur battery anode material provided by the invention uses lithium-sulphur cell positive electrode active material conduct provided by the invention
Positive electrode active materials improve the electric conductivity of positive electrode, so that lithium-sulfur cell is able to maintain higher specific capacity, follow
Ring stability significantly improves.
According to the fourth aspect of the present invention, the present invention provides a kind of lithium-sulfur cells, including lithium sulphur provided by the invention
Battery anode active material, the anode being prepared according to the preparation method of lithium-sulphur cell positive electrode active material provided by the invention
Active material or lithium-sulphur cell positive electrode active material provided by the invention.
Lithium-sulfur cell provided by the invention is using lithium-sulphur cell positive electrode active material provided by the invention as positive-active
Material can not only keep higher specific capacity, and cyclical stability significantly improves.
Technical solution provided by the invention is further described below with reference to embodiment and comparative example.
Embodiment 1
A kind of lithium-sulphur cell positive electrode active material is present embodiments provided, including being sintered the lithium sulfide of connection and doped with sulphur
The carbon material of element, is prepared in accordance with the following steps:
(1) poly- 3- hexyl thiophene (the weight average molecular weight amount 10 of 1g is weighed5G/mol), it is dissolved in 50ml tetrahydrofuran solvent
In；
(2) 5gLi is weighed2S ultrasonic disperse is in 50ml tetrahydrofuran solvent；
(3) step (1) and step (2) acquired solution are mixed, 800r/min magnetic agitation 30min；
Under the conditions of (4) 68 DEG C, tetrahydrofuran solvent rotary evaporation in step (3) is removed, solid is obtained；
(5) step (4) obtained solid is put into crucible, under protection of argon gas, is warming up to the heating rate of 2 DEG C/min
850 DEG C of heat preservation 1h to get arrive lithium-sulfur cell active material.
Embodiment 2
A kind of lithium-sulphur cell positive electrode active material is present embodiments provided, is prepared in accordance with the following steps:
(1) poly- 3- hexyl thiophene (the weight average molecular weight amount 10 of 1g is weighed5G/mol), it is dissolved in 50ml tetrahydrofuran solvent
In；
(2) 0.05g carbon nanotube and 5gLi are weighed respectively2S ultrasonic disperse is in 50ml tetrahydrofuran solvent；
(3) step (1) and step (2) acquired solution are mixed, 800r/min magnetic agitation 30min；
Under the conditions of (4) 68 DEG C, tetrahydrofuran solvent rotary evaporation in step (3) is removed, solid is obtained；
(5) step (4) obtained solid is put into crucible, under protection of argon gas, is warming up to the heating rate of 2 DEG C/min
850 DEG C of heat preservation 1h to get arrive lithium-sulfur cell active material.
Embodiment 3
A kind of lithium-sulphur cell positive electrode active material is present embodiments provided, is prepared in accordance with the following steps:
(1) 1g polyphenylene sulfide (weight average molecular weight amount 10 is weighed5G/mol), it is dissolved in 50mlNMP (N-Methyl pyrrolidone)
In solvent；
(2) 0.05g graphene and 5gLi are weighed respectively2S ultrasonic disperse is in 50ml tetrahydrofuran solvent；
(3) step (1) and step (2) acquired solution are mixed, 800r/min magnetic agitation 30min；
Under the conditions of (4) 203 DEG C, nmp solvent rotary evaporation in step (3) is removed, solid is obtained；
(5) step (4) obtained solid is put into crucible, under protection of argon gas, is warming up to the heating rate of 2 DEG C/min
850 DEG C of heat preservation 1h to get arrive lithium-sulfur cell active material.
Embodiment 4
A kind of lithium-sulphur cell positive electrode active material is present embodiments provided, is prepared in accordance with the following steps:
(1) 1g polyether sulfone (weight average molecular weight amount 10 is weighed5G/mol), it is dissolved in 50ml tetrahydrofuran solvent；
(2) 0.05g graphene oxide and 5gLi are weighed respectively2S ultrasonic disperse is in 50ml tetrahydrofuran solvent；
(3) step (1) and step (2) acquired solution are mixed, 800r/min magnetic agitation 30min；
Under the conditions of (4) 68 DEG C, tetrahydrofuran solvent rotary evaporation in step (3) is removed, solid is obtained；
(5) step (4) obtained solid is put into crucible, under protection of argon gas, is warming up to the heating rate of 2 DEG C/min
850 DEG C of heat preservation 1h to get arrive lithium-sulfur cell active material.
Comparative example 1
This comparative example provides a kind of lithium-sulphur cell positive electrode active material, the difference of preparation method and embodiment 1
It is, in step (1), poly- 3- hexyl thiophene is replaced using polyacrylonitrile.
Comparative example 2
This comparative example provides a kind of lithium-sulphur cell positive electrode active material, the difference of preparation method and embodiment 2
It is, in step (1), poly- 3- hexyl thiophene is replaced using polyacrylonitrile.
Comparative example 3
This comparative example provides a kind of lithium-sulphur cell positive electrode active material, the difference of preparation method and embodiment 2
It is, in step (1), poly- 3- hexyl thiophene is replaced using phenolic resin.
Comparative example 4
This comparative example provides a kind of lithium-sulphur cell positive electrode active material, the difference of preparation method and embodiment 2
It is, in step (1), poly- 3- hexyl thiophene is replaced using epoxy resin.
Comparative example 5
This comparative example provides a kind of lithium-sulphur cell positive electrode active material, the difference of preparation method and embodiment 2
It is, does not carry out step (1) and step (3), i.e., sulfurous organic compound is not added in raw material.
Embodiment 5-8
Embodiment 5-8 each provides a kind of lithium sulfur battery anode material, respectively includes the lithium sulphur electricity of embodiment 1-4 offer
Pond positive electrode active materials, conductive black and adhesive (polyacrylic acid), and the mass ratio of three is 8:1:1.
Comparative example 6-10
Comparative example 6-10 each provides a kind of lithium sulfur battery anode material, respectively includes the lithium sulphur of comparative example 1-5 offer
Battery anode active material, conductive carbon black and adhesive (polyacrylic acid), and the mass ratio of three is 8:1:1.
Embodiment 9-12
Embodiment 9-12 each provides a kind of lithium-sulfur cell, respectively by positive plate, to electrode lithium foil, diaphragm and electrolysis
Liquid is assembled, wherein the positive electrode that positive plate is provided by embodiment 5-8 respectively is coated on aluminium foil and is prepared.
Comparative example 11-15
Comparative example 11-15 each provides a kind of lithium-sulfur cell, respectively by positive plate, to electrode lithium foil, diaphragm and electricity
Solution liquid is assembled, wherein the positive electrode that positive plate is provided by comparative example 6-10 respectively is coated on aluminium foil and is prepared.
Test example 1
The lithium-sulfur cell that embodiment 9-12 and comparative example 10-15 are provided is subjected to specific capacity respectively and 80% cycle life is surveyed
Examination, the results are shown in Table 1.
1 lithium-sulfur cell performance data table of table
| Gram volume (mAh/g) | 80% cycle life (week) | |
| Embodiment 9 | 950 | 350 |
| Embodiment 10 | 1073 | 400 |
| Embodiment 11 | 1027 | 380 |
| Embodiment 12 | 995 | 380 |
| Comparative example 11 | 868 | 150 |
| Comparative example 12 | 968 | 200 |
| Comparative example 13 | 890 | 180 |
| Comparative example 14 | 833 | 150 |
| Comparative example 15 | 910 | 30 |
As it can be seen from table 1 the gram volume and cycle life of the lithium-sulfur cell that embodiment 9 provides are all remarkably higher than comparative example
11, this illustrates that the lithium-sulfur cell that embodiment 9 provides is mutually compound with the carbon material doped with element sulphur by using lithium sulfide
Positive electrode active materials, gram volume and cyclical stability are all remarkably higher than undoped lithium sulfide positive electrode active materials.
It can be seen that lithium-sulfur cell by using lithium sulfide and conductive materials from the comparison of embodiment 10-12 and embodiment 9
And significantly improved doped with its gram volume of the mutually compound positive electrode active materials of the carbon material three of element sulphur and cyclical stability, it is bright
It is aobvious to be higher than using lithium-sulfur cell made of the mutually compound positive electrode of both lithium sulfide and carbon material doped with element sulphur.
It can be seen that by using lithium sulfide and conductive materials and mix from the comparison of embodiment 10-12 and comparative example 12-15
The mutually compound positive electrode active materials of the miscellaneous carbon material for having element sulphur, can not only keep higher specific capacity, and stable circulation
Property significantly improves.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of lithium-sulphur cell positive electrode active material, which is characterized in that including being sintered the lithium sulfide of connection and doped with element sulphur
Carbon material.
2. lithium-sulphur cell positive electrode active material according to claim 1, which is characterized in that further include conductive materials；Wherein,
The conductive materials, lithium sulfide and the carbon material doped with element sulphur are sintered connection.
3. a kind of preparation method of lithium-sulphur cell positive electrode active material, which comprises the steps of:
After mixing by lithium sulfide and sulfurous organic compound, or by sulfide, sulfurous organic compound and conductive materials after mixing,
It is roasted to get lithium-sulphur cell positive electrode active material is arrived；Wherein,
In the lithium-sulphur cell positive electrode active material, lithium sulfide and the carbon material doped with element sulphur are sintered connection；Or
Lithium sulfide and doped with element sulphur carbon material and conductive materials be sintered connection.
4. preparation method according to claim 3, which is characterized in that be first dissolved separately in lithium sulfide and sulfurous organic compound
Solvent is removed in solvent after mixing, or first lithium sulfide, sulfurous organic compound and conductive materials are dissolved separately in solvent and are mixed
Solvent is removed after closing uniformly, obtains persursor material；
Persursor material is roasted again, obtains lithium-sulphur cell positive electrode active material.
5. preparation method according to claim 3, which is characterized in that the sulfurous organic compound is containing carbon and sulphur member
The polymer of element；
Preferably, the polymer containing carbon and element sulphur is the polymer containing carbon and element sulphur on main chain；
Preferably, the polymer containing carbon and element sulphur is selected from least one of polythiophene, polysulfones and polythiaether.
6. preparation method according to claim 3, which is characterized in that the conductive materials be selected from carbon nanotube, carbon fiber,
At least one of graphene, graphene oxide and conductive black.
7. preparation method according to claim 3, which is characterized in that roasted under inert gas protection；
Preferably, when roasting, heating rate is 1-5 DEG C/min, rises to 600-1000 DEG C, keeps the temperature 0.5-3h to get electric to lithium sulphur
Pond positive electrode active materials.
8. the preparation method according to claim 4, which is characterized in that the solvent is selected from N-Methyl pyrrolidone, tetrahydro
At least one of furans, chloroform, toluene, dimethylbenzene, dichloro-benzenes or dimethyl sulfoxide.
9. a kind of lithium sulfur battery anode material, which is characterized in that including positive electrode active materials of any of claims 1 or 2 or root
The positive electrode active materials for wanting any one of 3-8 preparation method to obtain according to right.
10. a kind of lithium-sulfur cell, which is characterized in that including positive electrode active materials of any of claims 1 or 2, or including basis
The positive electrode active materials that any one of the claim 3-8 preparation method obtains, or including lithium-sulfur cell as claimed in claim 9
Positive electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810805508.7A CN108987714B (en) | 2018-07-20 | 2018-07-20 | Lithium-sulfur battery positive electrode active material and preparation method thereof, lithium-sulfur battery positive electrode material and lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810805508.7A CN108987714B (en) | 2018-07-20 | 2018-07-20 | Lithium-sulfur battery positive electrode active material and preparation method thereof, lithium-sulfur battery positive electrode material and lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108987714A true CN108987714A (en) | 2018-12-11 |
| CN108987714B CN108987714B (en) | 2020-09-08 |
Family
ID=64549029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810805508.7A Active CN108987714B (en) | 2018-07-20 | 2018-07-20 | Lithium-sulfur battery positive electrode active material and preparation method thereof, lithium-sulfur battery positive electrode material and lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108987714B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105977488A (en) * | 2015-03-13 | 2016-09-28 | 现代自动车株式会社 | Method for manufacturing positive active material for all-solid lithium-sulfur battery |
| CN106159221A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of nano-sized carbon sulfur composite for lithium-sulfur cell |
| CN106299307A (en) * | 2016-09-30 | 2017-01-04 | 上海空间电源研究所 | A kind of lithium-sulfur cell high-performance positive electrode and preparation method thereof |
| CN107026260A (en) * | 2016-02-02 | 2017-08-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of lithium sulfide/carbon nano-composite material, its preparation method and application |
| JP2017216054A (en) * | 2016-05-30 | 2017-12-07 | トヨタ自動車株式会社 | Method for manufacturing lithium sulfur battery |
-
2018
- 2018-07-20 CN CN201810805508.7A patent/CN108987714B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105977488A (en) * | 2015-03-13 | 2016-09-28 | 现代自动车株式会社 | Method for manufacturing positive active material for all-solid lithium-sulfur battery |
| CN106159221A (en) * | 2015-04-27 | 2016-11-23 | 中国人民解放军63971部队 | A kind of nano-sized carbon sulfur composite for lithium-sulfur cell |
| CN107026260A (en) * | 2016-02-02 | 2017-08-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of lithium sulfide/carbon nano-composite material, its preparation method and application |
| JP2017216054A (en) * | 2016-05-30 | 2017-12-07 | トヨタ自動車株式会社 | Method for manufacturing lithium sulfur battery |
| CN106299307A (en) * | 2016-09-30 | 2017-01-04 | 上海空间电源研究所 | A kind of lithium-sulfur cell high-performance positive electrode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108987714B (en) | 2020-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106025200A (en) | Preparation method and application of nitrogen-doped MXene battery anode material | |
| CN108598390A (en) | A kind of preparation method and lithium-sulfur cell of positive material for lithium-sulfur battery | |
| CN106505204B (en) | A kind of lithium-sulphur cell positive electrode binder and preparation method thereof | |
| CN102447113A (en) | Lithium battery with polymer-coated sulfur/carbon composite material as anode | |
| CN108394884A (en) | A kind of preparation method of chitosan-based high-specific surface area nitrogen/phosphor codoping carbon nanosheet | |
| CN106920936B (en) | High-performance organic lithium ion battery positive electrode material and preparation method thereof | |
| CN111370702B (en) | Application of self-supporting porous hollow carbon fiber membrane | |
| CN114005969A (en) | Metal ion doped modified sodium ion material and preparation method and application thereof | |
| CN107221660A (en) | A kind of flexible lithium sulfur battery anode material | |
| CN105244474A (en) | High-specific capacity lithium-sulfur secondary battery composite cathode and preparation method thereof | |
| CN110148739A (en) | A kind of carbon@allyl sulfides itrile group polymer composite anode active material, anode and its preparation and the application in lithium-sulfur cell | |
| Zeng et al. | A multifunctional zipper-like sulfur electrode enables the stable operation of lithium-sulfur battery through self-healing chemistry | |
| CN109244393A (en) | A kind of lithium sulfur battery anode material and preparation method thereof of long circulating high rate capability | |
| CN109962224A (en) | A kind of three-dimensional carbon nanosheet-zinc oxide composites and the preparation method and application thereof | |
| CN110137462A (en) | Preparation method for aluminium/lithium sulphide battery vulcanization lithium/carbon composite material | |
| CN106684340A (en) | Lithium ion battery positive paste and preparation method thereof | |
| Hu et al. | Lithium-ion modified cellulose as a water-soluble binder for Li-O2 battery | |
| CN108987714A (en) | Lithium-sulphur cell positive electrode active material and preparation method thereof, lithium sulfur battery anode material and lithium-sulfur cell | |
| CN115498183A (en) | Modified vanadium manganese sodium phosphate cathode material, preparation and application thereof | |
| CN112599754B (en) | Polymer modified composite positive electrode for lithium-sulfur battery and preparation method thereof | |
| CN113571702A (en) | Positive electrode matrix material of quasi-solid-state lithium-sulfur battery and preparation method and application thereof | |
| CN102916188B (en) | Preparation method of hierarchical porous carbon/organo polysulfide/polyaniline composite material | |
| CN111036095A (en) | Flexible self-supporting MoO2@ C nanofiber film material and preparation method and application thereof | |
| CN108232162B (en) | Lithium-sulfur battery electrode material and preparation method thereof | |
| CN114361403B (en) | Method for preparing lithium sulfide electrode based on electrochemical means |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190702 Address after: 101102 Beijing Tongzhou District Huanyu Road No.3 Building No.14, 3 Floors Applicant after: Sander New Energy Technology Development Co.,Ltd. Applicant after: SOUNDON NEW ENERGY TECHNOLOGY Co.,Ltd. Address before: Unit 402, Fuqing Huayuan Commercial and Residential Building, Bayi Town, Linzhi City, Tibet Autonomous Region Applicant before: Sound Group Co.,Ltd. Applicant before: SOUNDON NEW ENERGY TECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201030 Address after: 411201 Xiangtan 316, Hunan, China, two, 316, Benz West Road. Patentee after: SOUNDON NEW ENERGY TECHNOLOGY Co.,Ltd. Address before: 101102 Beijing Tongzhou District Huanyu Road No.3 Building No.14, 3 Floors Patentee before: Sander New Energy Technology Development Co.,Ltd. Patentee before: SOUNDON NEW ENERGY TECHNOLOGY Co.,Ltd. |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20230426 Granted publication date: 20200908 |