CN105958031A - Sulfur-based cathode composite material and preparation method thereof - Google Patents
Sulfur-based cathode composite material and preparation method thereof Download PDFInfo
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- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a sulfur-based cathode composite material and a preparation method thereof. The sulfur-based cathode composite material is represented as (S-R1/MCM-41)R2, in which MCM-41 is a molecular sieve and is a cathode material base body; S is elemental sulfur and is an active constituent; R1 is a conducting polymer, is formed through a synthetic reaction of monomers thereof inside pore channels of the molecular sieve, and serves as a conducting agent and a sulfur-fixing agent; and R2 is a conducting substance, and is coated on the surface of composite material S-R1/MCM-41. The obtained cathode material is charged and discharged under 400 mA.g<-1>, and the first specific discharge capacity is 1390.5 mAh.g<-1> at most; by taking polyaniline as the conducting agent inside the molecular sieve and polypyrrole as the conducting substance, the sulfur-based cathode composite material synthetized by coating outside the material has higher circulation stability performance, the first specific discharge capacity of an assembled battery is 1191.9 mAh.g<-1>, and the capacity retention ratio after 200 times of circulation is 52.17%.
Description
Technical field
The invention belongs to new energy materials field, particularly relate to a kind of based on molecular sieve MCM-41, sulfur and
Sulfur-based positive electrode composite that conducting polymer is compound and preparation method thereof.
Background technology
Lithium ion battery is as a kind of new forms of energy energy storage device that can be recycled, and it has been subject to since being commercially used
To paying close attention to greatly.Along with environmental problem and the sternness increasingly of energy problem, lithium ion battery becomes the latentest
Power alleviating energy crisis and the important technology approach of control environmental pollution, compared to other type of secondary cell,
Output voltage is high, energy density is big, self-discharge rate is low, length in service life, ring owing to having for lithium ion battery
The advantages such as environment pollution is little and be widely studied, its purposes is more and more extensive.
Positive electrode used by conventional lithium ion battery mainly has cobalt acid lithium (LiCoO2), nickel-cobalt-manganese ternary
(LiNi1-x-yMnxCoyO2) and LiFePO4 (LiFePO4) etc..LiCoO2Theoretical capacity is 274mAh g-1,
But actual capacity only has 140mAh g-1, nickel-cobalt-manganternary ternary anode material actual specific capacity is up to
180mAh·g-1, LiFePO4Theoretical specific capacity be 170mAh g-1.Along with constantly carrying of social life level
Height, secondary energy storage battery capacity demand is also improved constantly by people, and traditional positive electrode holds owing to it is theoretical
Amount limits and is difficult to satisfy the needs of the people, and therefore, searching more cleaning, safety, theoretical capacity are higher
Positive electrode is the most very urgent.Composite positive pole lithium-sulfur rechargeable battery with elemental sulfur as active component, because of
Its theoretical energy density is up to 2600Wh kg-1, it is more than 3 times of conventional lithium ion battery and becomes and grind now
The focus and emphasis studied carefully.
Li-S secondary cell composite positive pole material with elemental sulfur as active component, it is except theoretical energy density
Outside high, also Sulphur ressource is abundant, cheap, nontoxic, advantages of environment protection, therefore, and lithium sulfur electricity
In pond, the composite positive pole with elemental sulfur as active component is considered as the one of following cell positive material development
Individual important directions (S.Evers, L.F.Nazar, Acc.Chem.Res., 2013,46 (5), 1135-1143).But,
It there is also some defects, as under elemental sulfur room temperature, for insulator, (under room temperature, conductivity is
5×10-30S/cm)；In elemental sulfur positive electrode, the content of sulfur is difficult to reach industrial requirement；Battery is in discharge and recharge
During can generate many lithium sulfides, many lithium sulfides can dissolve in the electrolytic solution, gathers negative pole by electrolyte
Lithium metal reaction with on negative pole, causes " effect of shuttling back and forth "；Lithium dendrite arm is easily caused as negative pole using lithium metal
Etc. a series of problem, these problems all affect the process of industrialization of lithium-sulfur cell.In order to solve lithium sulfur electricity
Problem present in pond, the improvement of battery performance is concentrated mainly on and improves sulfur-based positive electrode material by researchers
Electric conductivity and stability, the loss of inhibitory activity component sulfur, stop the dissolving in the electrolytic solution of many lithium sulfides and
Several aspects such as the growth preventing lithium dendrite arm.
Summary of the invention
The invention aims to overcome the problems referred to above, it is provided that a kind of based on molecular sieve MCM-41, sulfur and
Li-S cell positive material that conducting polymer is compound and preparation method thereof, this material is with elemental sulfur for activity group
Point, by with molecular sieve MCM-41 as framework material, the strong absorbability absorption utilizing molecular sieve pore passage is many
Lithium sulfide, is coated with one layer of conductive materials at material outer simultaneously, reduces the dissolution in the material of many lithium sulfides,
Suppression " effect of shuttling back and forth ", also solves the volume that in charge and discharge process, positive electrode causes because of the loss of elemental sulfur
Variation issue；First this preparation method synthesizes a small amount of conducting polymer in molecular sieve pore passage, it is achieved material
Inner conductive, then use chemical reduction method synthesis nano elemental sulfur, at mechanical agitation and ultrasound wave
Under effect, elemental sulfur it is immobilized on uniformly in molecular sieve pore passage and on conducting polymer materials, has synthesized load
Sulfur compound, then, is coated with one layer of conductive materials on sulfur compound material carrying, it is achieved material inside and outside
Portion conducts electricity simultaneously, improves electric conductivity and the utilization rate of elemental sulfur, is successfully obtained height ratio capacity, high rate capability
With the lithium sulfur battery anode material of long circulating stability, the supported quantity of its sulfur may be up to 71%.
To achieve these goals, the present invention uses following technical proposals:
A kind of sulfur-based positive electrode composite, it is characterised in that this sulfur-based positive electrode composite is expressed as
(S-R1/MCM-41)R2, wherein MCM-41 is molecular sieve, as the matrix of positive electrode；S is single
Matter sulfur, for active component；R1For conducting polymer, occurred synthesis anti-by monomer whose inside molecular sieve pore passage
Should, for conductive agent and sulphur-fixing agent；R2For conductive materials, it is coated on composite S-R1/ MCM-41 table
Face.
Further, described conducting polymer is the one in polyaniline, polypyrrole and polythiophene, corresponding
Conducting polymer monomer be aniline, pyrroles and thiophene.
Further, described conductive materials is metal-oxide or conducting polymer, described burning
Thing is titanium dioxide, ferroso-ferric oxide, Red copper oxide；Conducting polymer is polythiophene, polyacetylene, poly-pyrrole
Cough up, polyhenylene, polyaniline and polyphenylene ethylene.
Further, the median particle diameter of MCM-41 is less than 10um, preferably 10nm-100nm；Specific surface area
More than 800m2/g；Pore volume scope control is at 1-2.5cm2/g。
The preparation method of above-mentioned sulfur-based positive electrode composite, comprises the steps:
(1) preparation of conducting polymer/MCM-41 composite: by MCM-41 molecular sieve and conducting polymer
Thing monomer is weighed by the mass ratio of 10～16:1 and is placed on ultrasonic disperse instrument ultrasonic 1～2h, then stands 6～8h,
Add solution A to be placed on water-bath, under nitrogen atmosphere, install mechanical stirring device and open machinery
Stirring, tail gas enters in the aqueous solution of sodium hydroxide, then, is added dropwise over catalyst, ice-water bath or water-bath
Heating (bath temperature is 0～30 DEG C), stands 2～6h after continuing stirring 20～24h, filters, at 60～80 DEG C
It is dried to obtain conducting polymer/MCM-41 composite (hereinafter referred to as composite)；
(2) solid sulfur: use the one in vacuum heat method, protective atmosphere heat treating process or chemical method to leading
Electric polymer/MCM-41 composite carries out solid sulfur, obtains carrying sulfur compound；
(3) cladding of conductive materials: carrying sulfur compound outer cladding conductive materials, obtains sulfur-based positive electrode and is combined
Material.
Further, described conducting polymer monomer is that aniline, pyrroles and thiophene (correspond respectively to conduction
Polymer polyanaline, polypyrrole and polythiophene), corresponding solution A be hydrochloric acid, lignin sulfonic acid sodium solution and
Chloroform, the catalyst used by synthesized polyaniline is Ammonium persulfate., the catalysis used by synthesis polypyrrole and polythiophene
Agent is iron chloride
In step (2), the step of the solid sulfur of chemical method is as follows: a, under nitrogen protection, uses sodium thiosulfate
Generate elemental sulfur with hydrochloric acid reaction, under ultrasound wave and mechanical agitation, elemental sulfur is immobilized on composite
In (conducting polymer/molecular sieve MCM-41), filter, be dried；B, the most under vacuum conditions heat by
The elemental sulfur distillation that material surface adsorption is weak, is cooled to room temperature.
In step a, sodium thiosulfate controls with the mass ratio of composite (conducting polymer/MCM-41)
10～20:1, the concentration range of hydrochloric acid is 1.3～1.5mol/L, and pH controls 7～7.5；Response time controls
24～48h, baking temperature controls at 60～80 DEG C；In step b, vacuum ranges, 0.1～100Pa, adds
Hot temperature at 80～110 DEG C, persistent period 20min-40min.
Further, the conductive materials thickness of cladding is 1nm～1 μm, preferably 10nm～80nm.
The present invention compared with prior art, has the advantages that
(1) molecular sieve MCM-41 is applied to lithium-sulfur cell field, at home and abroad document, patent by the present invention
In have no relevant report.The present invention use the MCM-41 of small-bore structure as framework material, this aperture
Many lithium sulfides that material is produced in charge and discharge process by structure have the strongest absorbability, can effectively press down
System " effect of shuttling back and forth ", and reduce material in charge and discharge process owing to sulfur mass change causes bulk effect not
Profit impact, meanwhile, the molecular sieve of small-bore structure is conducive to controlling the size of elemental sulfur, prevents simple substance
Sulfur is assembled.
(2) present invention firstly provides the idea simultaneously conducted electricity in the inside and outside portion of sulfur-based positive electrode material, first existed
Molecular sieve internal gutter synthesizes a small amount of conducting polymer, then elemental sulfur is immobilized on molecular sieve internal and
On conducting polymer, this quantity being conducive to increasing material internal elemental sulfur conduction, elemental sulfur is greatly improved
Chemical property, then it is coated with one layer of conductive materials, lithium-sulphur cell positive electrode prepared by this method at material surface
Material, has the property that the inside and outside portion of material conducts electricity simultaneously, can improve the utilization rate of elemental sulfur greatly,
Thus be successfully obtained big specific capacity, long circulating stability and the electrode of high rate capability, and material is repeatedly
In charge and discharge process, the loss amount of sulfur is few, material circulation excellent performance.
(3) positive electrode prepared by the inventive method, at 400mA g-1Lower discharge and recharge, discharge specific volume first
Amount is up to 1390.5mAh g-1；With polyaniline for molecular sieve inner conductive agent, polypyrrole is conductive materials,
The sulfur-based positive electrode material list being coated on material outer and synthesize reveals preferable stable circulation performance, with this material
The first discharge specific capacity being assembled into battery is 1191.9mAh g-1, after circulating 200 times, capability retention is
52.17%.
(4) the inventive method preparation technology is simple, it is not necessary to the special handlings such as high temperature, and cheaper starting materials is easy to get, and produces
Thing is evenly distributed, and is especially suitable for large-scale production, has great industrial application value.
Accompanying drawing explanation
The method that Fig. 1 is the embodiment of the present invention 1, embodiment 2 and comparative example are provided prepares lithium-sulphur cell positive electrode
The XRD diffraction pattern of material；
Fig. 2 is the battery first charge-discharge schematic diagram after the positive electrode prepared by the embodiment of the present invention 1 assembles；
Fig. 3 is the electric discharge of circulating battery after positive electrode prepared by the embodiment of the present invention 1 assembles 250 times
Capacity curve figure.
Detailed description of the invention
The following examples are to be clearly and completely described the technical scheme in the embodiment of the present invention, aobvious
So, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on
Embodiments of the invention, those of ordinary skill in the art are obtained under not making creative work premise
Every other embodiment, broadly falls into protection scope of the present invention.
Embodiment 1
The preparation of PAN/MCM-41 composite: the particle size range choosing small-bore molecular sieve MCM-41 is
10nm-100nm, selects this particle size range to be conducive to controlling the particle diameter of elemental sulfur during follow-up synthesis elemental sulfur
In nanometer range, prevent the gathering of elemental sulfur.MCM-41 and aniline 12:1 in mass ratio is weighed
(MCM-41 weighs 2g) is placed in ultrasonic 2h on ultrasonic disperse instrument, stands 6h afterwards, adds 1.4mol/L's
Hydrochloric acid solution 5ml is placed under nitrogen atmosphere, and tail gas enters in the aqueous solution of sodium hydroxide, mechanical agitation 2h,
It is added dropwise over the Ammonium persulfate. 2ml of 0.8mol/L, is transferred in water-bath and is heated to 16 DEG C, continue stirring 20h,
Close stirring, after standing 2h, obtain conducting polymer PAN/MCM-41 composite mixed solution.
S-PAN/MCM-41 carries the preparation of sulfur composite: be placed under Vltrasonic device by above-mentioned mixed solution,
Nitrogen atmosphere is protected, and exhaust gas processing device is constant, adds the aqueous solution dissolved with 20～40g sodium thiosulfate,
Mechanical agitation 2h under ultrasonication, adds the hydrochloric acid of 1.4mol/L, regulates pH to 7, after continuing stirring 6h,
The mixed solution of gained is stood in ice-water bath 24h, filters, with deionized water and absolute ethanol washing repeatedly
Obtain solid, gained solid is placed in baking oven at 60 DEG C and is dried 8h, then, be placed in vacuum drying oven
Being dried under uniform temperature, vacuum degree control is 0.1～100Pa, and temperature range controls at 80～110 DEG C, when being dried
Between elemental sulfur that to be 0.5h weak to remove material surface absorption affinity, after be cooled to room temperature, solid is ground to sieve
After must carry sulfur composite S-PAN/MCM-41.
(S-PAN/MCM-41) preparation of PPy sulfenyl composite: the 3.0g weighing above-mentioned preparation carries sulfur
Composite, is scattered in 50ml ethanol solution, adds appropriate cetyl trimethylammonium bromide, and machinery stirs
Mixing 6～8h, to strengthen the surface activity of molecular sieve, joined in above-mentioned solution by 0.5g polypyrrole, machinery stirs
Mix 16h, by solution sucking filtration, respectively clean 3 times with ethanol and deionized water, put in drying baker permanent at 60 DEG C
Temperature 12h, obtains load sulfur materials (S-PAN/MCM-41) PPy of polymer overmold.
Embodiment 2
The preparation of PPy/MCM-41 composite: the particle size range choosing mesostructured material is
10nm-100nm, is dispersed in 2g molecular sieve MCM-41 in the aqueous solution dissolved with 5g lignin sodium, uses pin
Pipe injection 0.17g newly steams pyrroles and is placed on ultrasonic 2h on ultrasonic disperse instrument, stands 6h afterwards, adds 2mL concentration
Being placed under nitrogen atmosphere for 0.5mol/L ferric chloride solution, tail gas enters in the aqueous solution of sodium hydroxide, puts
Mechanical agitation 20h on ice-water bath, closes stirring, after standing 2h, obtains the conducting polymer of Supported on Zeolite
PPy/MCM-41 composite mixed solution.
S-PPy/MCM-41 carries the preparation method of sulfur composite and carries sulfur composite with above-described embodiment 1
The preparation method of S-PAN/MCM-41 is identical.
(S-PPy/MCM-41) preparation of PTh sulfenyl composite: the 3.0g weighing above-mentioned preparation carries sulfur again
Condensation material, is scattered in 50ml ethanol solution, adds appropriate cetyl trimethylammonium bromide, mechanical agitation
6～8h, to strengthen the surface activity of molecular sieve, 0.5g polythiophene is joined in above-mentioned solution, mechanical agitation
16h, by solution sucking filtration, respectively cleans 3 times with ethanol and deionized water, puts in drying baker constant temperature at 60 DEG C
12h, obtains composite (S-PPy/MCM-41) PTh of polythiophene cladding.
Embodiment 3
(S-PAN/MCM-41)TiO2The preparation of sulfenyl composite: carry sulfur material according to synthesis in embodiment 1
Material S-PAN/MCM-41 through filtering, dried, weigh load sulfur materials S-PAN/MCM-41:TiO2Quality
Ratio joins in ball mill for 6:1, and under an inert atmosphere, the rotating speed of ball mill is 1000 revs/min, during ball milling
Between be 4 hours, prepare thing subsequently under 5C, be dried 6h, cool down, sieve after the sulfur of coated by titanium dioxide
Base anode material (S-PAN/MCM-41) TiO2。
Comparative example 1
Increase the effect of electric conductivity for showing material inside, prepare as follows without molecular sieve inner conductive
The positive electrode of agent.
S-MCM-41 carries the preparation of sulfur materials: protecting at nitrogen atmosphere, tail gas enters the aqueous solution of sodium hydroxide
In, 2g molecular sieve MCM-41 is dispersed in 80mL aqueous solution, adds dissolved with 20～40g thiosulfuric acids
The aqueous solution of sodium, mechanical agitation 2h under ultrasonication, add the hydrochloric acid of 1.4mol/L, regulate pH to 7～7.5,
Continue stirring 6h after, the mixed solution of gained is stood in ice-water bath 24h, filter, with deionized water with
Gained solid repeatedly, is placed in baking oven at 60 DEG C and is dried 8h, then, be placed in vacuum by absolute ethanol washing
Being dried at a certain temperature in drying baker, vacuum degree control is 1～100Pa, and temperature range controls 80～110
DEG C, drying time 0.5h with remove material surface absorption elemental sulfur, after be cooled to room temperature, solid is through grinding
Sulfur composite S-MCM-41 must be carried after honed sieve.
(S-MCM-41) preparation of PPy sulfenyl composite: the 3.0g weighing above-mentioned preparation carries sulfur composite wood
Material, is scattered in 50ml ethanol solution, adds appropriate cetyl trimethylammonium bromide, mechanical agitation 6h-8h,
To strengthen the surface activity of molecular sieve, 0.5g polypyrrole is joined in above-mentioned solution, mechanical agitation 16h,
By solution sucking filtration, respectively clean 3 times with ethanol and deionized water, put in drying baker constant temperature 12h under 60C,
Load sulfur materials (S-MCM-41) PPy to polypyrrole cladding.
After the sulfur-based positive electrode material of preparation in above example and comparative example, then positive electrode is prepared as
Electrode plates, sulfenyl composite active material, conductive agent and binding agent mass ratio 7:2:1 in pole piece preparation, wherein
Conductive agent is acetylene carbon black, and binding agent is Kynoar, and solvent is N-Methyl pyrrolidone, and collector is
Aluminium foil, is assembled into 2025 type button cells by pole piece, then tests the chemical property of battery, tests temperature
For room temperature, test multiplying power is 0.2C, and test voltage scope is 1.0～3.0V, and test result is as shown in table 1 below.
The electrical performance testing result of table 1 each embodiment gained positive electrode correspondence battery
Claims (9)
1. a sulfur-based positive electrode composite, it is characterised in that this sulfur-based positive electrode composite is expressed as
(S-R1/MCM-41)R2, wherein MCM-41 is molecular sieve, as the matrix of positive electrode；S is single
Matter sulfur, for active component；R1For conducting polymer, occurred synthesis anti-by monomer whose inside molecular sieve pore passage
Should, for conductive agent and sulphur-fixing agent；R2For conductive materials, it is coated on composite S-R1/ MCM-41 table
Face.
Sulfur-based positive electrode composite the most according to claim 1, it is characterised in that described conduction is gathered
Compound is the one in polyaniline, polypyrrole and polythiophene.
Sulfur-based positive electrode composite the most according to claim 1 and 2, it is characterised in that described leads
Isoelectric substance is metal-oxide or conducting polymer, and described metal-oxide is titanium dioxide, four oxidations three
One in ferrum, Red copper oxide；Conducting polymer is polythiophene, polyacetylene, polypyrrole, polyhenylene, gathers
One in aniline and poly-phenylene vinylene (ppv).
Sulfur-based positive electrode composite the most according to claim 3, it is characterised in that in MCM-41
Value particle diameter is more than 800m less than 10um, specific surface area2/ g, pore volume scope control is at 1-2.5cm2/g。
5. the preparation method of the sulfur-based positive electrode composite described in any one of Claims 1-4, its feature exists
In, comprise the steps:
(1) preparation of conducting polymer/MCM-41 composite: by MCM-41 molecular sieve and conducting polymer
The mass ratio of thing monomer 10～16:1 weighs and is placed on ultrasonic disperse instrument ultrasonic 1～2h, then stands 6～8h,
Add solution A to be placed on water-bath, under nitrogen atmosphere, install mechanical stirring device and open machinery
Stirring, tail gas enters in the aqueous solution of sodium hydroxide, then, is added dropwise over catalyst, ice-water bath or water-bath
Heating, stands 2～6h after continuing stirring 20～24h, filters, and is dried to obtain conducting polymer at 60～80 DEG C
/ MCM-41 composite；
(2) solid sulfur: use the one in vacuum heat method, protective atmosphere heat treating process or chemical method to leading
Electric polymer/MCM-41 composite carries out solid sulfur；
(3) cladding of conductive materials: carrying sulfur compound outer cladding conductive materials, obtains sulfur-based positive electrode and is combined
Material.
The preparation method of sulfur-based positive electrode composite the most according to claim 5, it is characterised in that step
Suddenly in (2), the step of the solid sulfur of chemical method is as follows: a, under nitrogen protection, uses sodium thiosulfate and hydrochloric acid
Reaction generates elemental sulfur, and elemental sulfur is immobilized under ultrasound wave and mechanical agitation composite (conduction
Polymer/molecular sieve MCM-41) in, filter, be dried；B, heat material list the most under vacuum conditions
The elemental sulfur distillation that face adsorption is weak, is cooled to room temperature.
The preparation method of sulfur-based positive electrode composite the most according to claim 6, it is characterised in that step
In rapid a, sodium thiosulfate controls 10～20:1 with the mass ratio of composite, and the concentration range of hydrochloric acid exists
1.3～1.5mol/L, pH control 7～7.5；Response time controls 24～48h, and baking temperature controls 60～80
℃；In step b, vacuum ranges 0.1～100Pa, heating-up temperature at 80～110 DEG C, persistent period 20min
-40min。
The preparation method of sulfur-based positive electrode composite the most according to claim 5, it is characterised in that bag
The conductive materials thickness covered is 1nm～1 μm.
The preparation method of sulfur-based positive electrode composite the most according to claim 5, it is characterised in that water
The temperature of bath heating is 0～30 DEG C.
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| CN106654226A (en) * | 2017-01-19 | 2017-05-10 | 上海德朗能动力电池有限公司 | High-capacity safe conductive high-polymer-coated elemental sulfur electrode material and manufacturing method thereof |
| CN106784728A (en) * | 2017-01-19 | 2017-05-31 | 上海德朗能动力电池有限公司 | Conduction high polymer cladding sulfur electrode material and its manufacture method of a kind of high-capacity secure |
| CN106848267A (en) * | 2017-04-10 | 2017-06-13 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2TxThe types of/MCM 41 are classified sulphur carbon composite |
| CN106876683A (en) * | 2017-04-10 | 2017-06-20 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2TxThe types of/KIT 1 are classified sulphur carbon composite |
| CN106920943A (en) * | 2017-04-10 | 2017-07-04 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2TxThe types of/SBA 15 are classified sulphur carbon composite |
| CN106941163A (en) * | 2017-04-10 | 2017-07-11 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2Tx/ MSU X-types are classified sulphur carbon composite |
| CN107195874A (en) * | 2017-04-19 | 2017-09-22 | 深圳市沃特玛电池有限公司 | A kind of preparation method of the Si-C composite material of polypyrrole cladding |
| CN111082012A (en) * | 2019-12-17 | 2020-04-28 | 桑顿新能源科技有限公司 | Silicon-aluminum-sulfur phosphate composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
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| CN106848267A (en) * | 2017-04-10 | 2017-06-13 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2TxThe types of/MCM 41 are classified sulphur carbon composite |
| CN106920943B (en) * | 2017-04-10 | 2019-11-15 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2Tx/ SBA-15 type is classified sulphur carbon composite |
| CN106876683B (en) * | 2017-04-10 | 2019-11-29 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2Tx/ KIT-1 type is classified sulphur carbon composite |
| CN107195874A (en) * | 2017-04-19 | 2017-09-22 | 深圳市沃特玛电池有限公司 | A kind of preparation method of the Si-C composite material of polypyrrole cladding |
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| CN111082012A (en) * | 2019-12-17 | 2020-04-28 | 桑顿新能源科技有限公司 | Silicon-aluminum-sulfur phosphate composite material, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
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