CN106876683A - A kind of Ti3C2TxThe types of/KIT 1 are classified sulphur carbon composite - Google Patents

A kind of Ti3C2TxThe types of/KIT 1 are classified sulphur carbon composite Download PDF

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CN106876683A
CN106876683A CN201710229675.7A CN201710229675A CN106876683A CN 106876683 A CN106876683 A CN 106876683A CN 201710229675 A CN201710229675 A CN 201710229675A CN 106876683 A CN106876683 A CN 106876683A
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carbon material
kit
carbon
reaction
sulphur
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CN106876683B (en
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钟玲珑
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Changshu intellectual property operation center Co., Ltd
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Shenzhen Pei Cheng Technology Co Ltd
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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
    • H01M4/362—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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Abstract

The present invention provides a kind of Ti3C2TxThe types of/KIT 1 are classified sulphur carbon composite, by the carbon material of spherical hierarchy, the Ti being dispersed in hierarchy carbon material3C2TxWith elemental sulfur composition, classification carbon material is in outer layer to elemental sulfur and Ti3C2TxCoated, wherein Ti3C2Tx：Carbon：The mass ratio of sulphur is 0.1 0.3：0.1‑0.3:1, classification carbon material is made up of the micro-pore carbon material of meso-porous carbon material and the organic carbon of external sheath.Ti in the composite3C2TxOn T be F groups or OH groups, highly polar group is with the oxygen of surface of graphene oxide, strong chemisorbed can be formed to the polysulfide formed in charge and discharge process, the micropore of porous carbon materials also can carry out physical absorption to polysulfide simultaneously, it is this while the ability with physics and chemisorbed can effectively prevent polysulfide from moving, the generation of shuttle effect is reduced, the life-span of lithium-sulfur cell is improved.

Description

A kind of Ti3C2Tx/ KIT-1 types are classified sulphur carbon composite
Technical field
The present invention relates to nano material synthesis, more particularly to a kind of preparation method of lithium sulfur battery anode material.
Background technology
Lithium-sulfur cell is that, with lithium metal as negative pole, elemental sulfur is the battery system of positive pole.Lithium-sulfur cell is put with two Level platform（About 2.4 V and 2.1 V）, but its electrochemical reaction mechanism is more complicated.Lithium-sulfur cell has specific energy high （2600 Wh/kg）, specific capacity it is high（1675 mAh/g）, low cost and other advantages, it is considered to be very promising a new generation's electricity Pond.But the problems such as there is low active material utilization, low cycle life and poor security at present, this seriously governs lithium The development of sulphur battery.Causing the main cause of above mentioned problem has the following aspects：（1）Elemental sulfur is electronics and ion insulation Body, room-temperature conductivity is low（5×10-30S·cm-1）, it is because the sulphur without ionic state is present thus tired as positive electrode activation It is difficult；（2）The many lithium sulfide Li of high poly- state produced in electrode process2Sn（8 ＞ n >=4）It is soluble in electrolyte, positive and negative Concentration difference is formed between pole, negative pole is moved in the presence of concentration gradient, the poly- many lithium sulfides of state high are reduced into low by lithium metal The poly- many lithium sulfides of state.The carrying out of reaction more than, the oligomeric many lithium sulfides of state are assembled in negative pole, are finally formed between electrodes Concentration difference, moves to positive pole and is oxidized to many lithium sulfides of poly- state high again.This phenomenon is referred to as shuttle effect, reduces sulphur activity The utilization rate of material.While insoluble Li2S and Li2S2Cathode of lithium surface is deposited on, lithium-sulfur cell is further degrading Performance；（3）Reaction final product Li2S is equally electronic body, can be deposited on sulfur electrode, and lithium ion vulcanizes in solid-state Migration velocity is slow in lithium, makes electrochemical reaction kinetic rate slack-off；（4）Sulphur and final product Li2The density of S is different, works as sulphur Rear volumetric expansion about 79% is lithiated, Li is easily caused2The efflorescence of S, causes the safety problem of lithium-sulfur cell.Above-mentioned not enough restriction The development of lithium-sulfur cell, this is also the Important Problems that current lithium-sulfur cell research needs to solve.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of Ti3C2Tx/ KIT-1 types are classified sulphur carbon composite, and this is answered Carbon material, the Ti that is dispersed in hierarchy carbon material of the condensation material by spherical hierarchy3C2TxWith elemental sulfur composition, classification Carbon material is in outer layer to elemental sulfur and Ti3C2TxCoated, wherein Ti3C2Tx：Carbon：The mass ratio of sulphur is 0.1-0.3：0.1- 0.3:1, classification carbon material is made up of the micro-pore carbon material of meso-porous carbon material and the organic carbon of external sheath.
The present invention provides a kind of Ti3C2TxThe preparation method of/KIT-1 types classification sulphur carbon composite is as follows：
（1）The silsesquioxane of 1.5mmol octaphenyls eight is added to 70mL 1, it is molten in 60 DEG C of mechanical agitations in 2- dichloroethanes Solution, adds Ti3AlC2Ceramic powders and KIT-1 powder, stirring form suspension；
（2）Added to addition 2mmol anhydrous Aluminum chlorides catalyst in suspension and 40 mL carbon tetrachloride crosslinking agents, stirring crosslinking Reaction 10h, after reaction terminates, adds ethanol/water solution, and ethanol/dilute hydrochloric acid solution is washed, washes, is vacuum dried, and obtains forerunner Body；
（3）Presoma is placed in the Muffle furnace of nitrogen atmosphere protection, the reaction of 900 DEG C 3h2 °C/min high temperature cabonizations；
（4）Product after carbonization is placed in hydrofluoric acid and is performed etching, solution addition deionized water is carried out at centrifugation after corrosion Reason, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
（5）By Ti3C2Tx/ spherical porous carbon material is well mixed with elemental sulfur, is positioned over 155-165 DEG C in the tube furnace of sealing Reaction 12 hours, is heated to 200 DEG C and is passed through nitrogen reaction 30 minutes, after natural cooling, obtains Ti3C2Tx/ sulphur carbon composite wood Material.
Step（1）The silsesquioxane of middle octaphenyl eight：The ratio of 1,2- dichloroethanes is 1g：50-100mL, stirring reaction Temperature is 50-70 DEG C, the silsesquioxane of octaphenyl eight and Ti3AlC2The mass ratio of ceramic powders is 1：0.05-0.5, octaphenyl eight Silsesquioxane is 1 with the mass ratio of KIT-1：0.05-0.5;
Step（2）Middle catalyst is anhydrous Aluminum chloride, and the quality of catalyst is the 5-10% of the silsesquioxane quality of octaphenyl eight, Crosslinking agent is carbon tetrachloride, and crosslinking agent quality is 10-40 times of the silsesquioxane quality of octaphenyl eight, and the stirring reaction time is 5-10 Hour, ethanol in ethanol/water solution：The volume ratio of water is 2-4：1, watery hydrochloric acid is for mass fraction in ethanol/dilute hydrochloric acid solution 10% hydrochloric acid solution, ethanol and watery hydrochloric acid volume ratio 2-4：1;
Step（3）Reaction atmosphere in middle Muffle furnace is nitrogen, and 800-1200 DEG C of reaction temperature reaction time 1-5 hours, heats up 1-5 °C/minute of speed；
Step（4）The concentration of middle hydrofluoric acid is 20%-50%, and the time of corrosion is 4-24 hours;
Step（5）Middle Ti3C2Tx/ spherical porous carbon material is 0.1-0.3 with the mass ratio of elemental sulfur：1, the initial stage is anti-in tube furnace It is 155-165 DEG C to answer temperature, and the reaction time is 10-20 hours, the reaction temperature after nitrogen is passed through for 180-200 DEG C, during reaction Between be 10-30 minutes.
The present invention has the advantages that：（1）Ti3C2TxThere is classification in/KIT-1 types classification sulphur carbon composite Pore structure, by substantial amounts of micropore and it is mesoporous constitute, it is internal it is mesoporous surrounded by outside micropore, the advantage of this structure is, Sulphur can be injected into the meso-hole structure of inside, and outside less micropore can as a physical barriers of limitation lithium polysulfide To provide effective storage sulphur space；（2）The carbon material of the composite external sheath effectively limits the motion of sulfenyl material, makes It is internally moved；（3）Ti in the composite3C2TxOn T be-F groups or-OH groups, with surface of graphene oxide Oxygen be highly polar group, can in charge and discharge process formed polysulfide form strong chemisorbed, while porous The micropore of carbon material can also carry out physical absorption to polysulfide, this while the ability with physics and chemisorbed can be effective Prevention polysulfide motion, reduce shuttle effect generation, improve lithium-sulfur cell life-span.
Brief description of the drawings
Fig. 1 is the preparation technology flow chart of composite of the present invention.
Fig. 2 is the charge-discharge performance figure of composite of the present invention.
Specific embodiment
Below in conjunction with the accompanying drawings, preferably embodiment of the invention is described in further detail：
Embodiment 1
（1）The silsesquioxane of 1g octaphenyls eight is added to 50mL 1, in 2- dichloroethanes, in 50 DEG C of mechanical agitation dissolvings, then Add 0.05gTi3AlC2Ceramic powders and 0.05g KIT-1 powder, stirring form suspension；
（2）To adding 0.05g anhydrous Aluminum chlorides catalyst and 10g carbon tetrachloride crosslinking agent to add in suspension, stirring crosslinking is anti- Answer 5 hours, after reaction terminates, add ethanol/water solution, ethanol/dilute hydrochloric acid solution is washed, washes, is vacuum dried, and obtains forerunner Body；
（3）Presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 800 DEG C of calcinings 5h, 1 °C/min of programming rate；
（4）Product after carbonization is placed in concentration to be etched 24 hours in 20% hydrofluoric acid, solution adds deionized water after corrosion Centrifugal treating is carried out, then sediment is dried, Ti is obtained3C2Tx/ spherical porous carbon material；
（5）By 0.1g Ti3C2Tx/ spherical porous carbon material is well mixed with 1g elemental sulfurs, is positioned over 165 in the tube furnace of sealing DEG C reaction 10 hours, be heated to 200 DEG C be passed through nitrogen react 10 minutes, after natural cooling, obtain Ti3C2Tx/ KIT-1 types point Level sulphur carbon composite.
Embodiment 2
（1）The silsesquioxane of 1g octaphenyls eight is added to 100mL 1, in 2- dichloroethanes, in 70 DEG C of mechanical agitation dissolvings, then Add 0. 5gTi3AlC2Ceramic powders and 0. 5g KIT-1 powder, stirring form suspension；
（2）To adding 0.1g anhydrous Aluminum chlorides catalyst and 40g carbon tetrachloride crosslinking agent to add in suspension, stirring crosslinking is reacted 10 hours, after reaction terminates, ethanol/water solution is added, ethanol/dilute hydrochloric acid solution is washed, washes, is vacuum dried, and obtains presoma；
（3）Presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 1200 DEG C of calcinings 1h, 5 °C/min of programming rate；
（4）Product after carbonization is placed in concentration to be etched 4 hours in 50% hydrofluoric acid, solution adds deionized water to enter after corrosion Row centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
（5）By 0.3g Ti3C2Tx/ spherical porous carbon material is well mixed with 1g elemental sulfurs, is positioned in the tube furnace of sealing 155 DEG C are reacted 20 hours, are heated to 180 DEG C and are passed through nitrogen reaction 30 minutes, after natural cooling, obtain Ti3C2Tx/ KIT-1 Type is classified sulphur carbon composite.
Embodiment 3
（1）The silsesquioxane of 1g octaphenyls eight is added to 70mL 1, in 2- dichloroethanes, in 60 DEG C of mechanical agitation dissolvings, then Add 0.1gTi3AlC2Ceramic powders and 0.2g KIT-1 powder, stirring form suspension；
（2）To adding 0.08g anhydrous Aluminum chlorides catalyst and 20g carbon tetrachloride crosslinking agent to add in suspension, stirring crosslinking is anti- Answer 8 hours, after reaction terminates, add ethanol/water solution, ethanol/dilute hydrochloric acid solution is washed, washes, is vacuum dried, and obtains forerunner Body；
（3）Presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 1000 DEG C of calcinings 3h, 3 °C/min of programming rate；
（4）Product after carbonization is placed in concentration to be etched 16 hours in 30% hydrofluoric acid, solution adds deionized water to enter after corrosion Row centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
（5）By 0.2g Ti3C2Tx/ spherical porous carbon material is well mixed with 1g elemental sulfurs, is positioned in the tube furnace of sealing 160 DEG C are reacted 15 hours, are heated to 190 DEG C and are passed through nitrogen reaction 20 minutes, after natural cooling, obtain Ti3C2Tx/ KIT-1 Type is classified sulphur carbon composite.
Embodiment 4
（1）The silsesquioxane of 1g octaphenyls eight is added to 80mL 1, in 2- dichloroethanes, in 65 DEG C of mechanical agitation dissolvings, then Add 0.2gTi3AlC2Ceramic powders and 0.4g KIT-1 powder, stirring form suspension；
（2）To adding 0.07g anhydrous Aluminum chlorides catalyst and 30g carbon tetrachloride crosslinking agent to add in suspension, stirring crosslinking is anti- Answer 6 hours, after reaction terminates, add ethanol/water solution, ethanol/dilute hydrochloric acid solution is washed, washes, is vacuum dried, and obtains forerunner Body；
（3）Presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 900 DEG C of calcinings 4h, 2 °C/min of programming rate；
（4）Product after carbonization is placed in concentration to be etched 10 hours in 40% hydrofluoric acid, solution adds deionized water to enter after corrosion Row centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
（5）By 0.15g Ti3C2Tx/ spherical porous carbon material is well mixed with 1g elemental sulfurs, is positioned in the tube furnace of sealing 158 DEG C are reacted 18 hours, are heated to 185 DEG C and are passed through nitrogen reaction 25 minutes, after natural cooling, obtain Ti3C2Tx/ KIT-1 Type is classified sulphur carbon composite.
Embodiment 5
（1）The silsesquioxane of 1g octaphenyls eight is added to 60mL 1, in 2- dichloroethanes, in 55 DEG C of mechanical agitation dissolvings, then Add 0.3gTi3AlC2Ceramic powders and 0.2g KIT-1 powder, stirring form suspension；
（2）To adding 0.09g anhydrous Aluminum chlorides catalyst and 25g carbon tetrachloride crosslinking agent to add in suspension, stirring crosslinking is anti- Answer 7 hours, after reaction terminates, add ethanol/water solution, ethanol/dilute hydrochloric acid solution is washed, washes, is vacuum dried, and obtains forerunner Body；
（3）Presoma is placed in the Muffle furnace of nitrogen atmosphere protection, 1100 DEG C of calcinings 2h, 4 °C/min of programming rate；
（4）Product after carbonization is placed in concentration to be etched 12 hours in 35% hydrofluoric acid, solution adds deionized water to enter after corrosion Row centrifugal treating, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
（5）By 0.25g Ti3C2Tx/ spherical porous carbon material is well mixed with 1g elemental sulfurs, is positioned in the tube furnace of sealing 1625 DEG C are reacted 13 hours, are heated to 195 DEG C and are passed through nitrogen reaction 20 minutes, after natural cooling, obtain Ti3C2Tx/ KIT-1 Type is classified sulphur carbon composite.
The preparation and performance test of electrode；By composite, acetylene black and PVDF in mass ratio 80：10：10 in NMP Mixing, it is electrode film to be coated on aluminium foil, and metal lithium sheet is that, to electrode, CELGARD 2400 is barrier film, the LiTFSI/ of 1mol/L DOL-DME (volume ratios 1:1) it is electrolyte, the LiNO3 of 1mol/L is additive, button electricity is assembled into full of Ar glove boxes Pond, constant current charge-discharge test is carried out using Land battery test systems.Charging/discharging voltage scope is 1-3V, and current density is 0.5C, performance is as shown in table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
First discharge specific capacity（mAh/g） 880 890 881 878 886
Fig. 2 is the charge-discharge performance figure that the composite of the embodiment of the present invention 1 is prepared into lithium-sulfur cell.As can be seen from the figure charge and discharge Electrical efficiency can reach more than 99%, and first charge-discharge capacity is 920 mAh/g, and efficiency for charge-discharge is 99.2%, 500 discharge and recharges After circulation, capacity still possesses 73%, illustrates the structure of the composite and can effectively suppress shuttle effect, improves the longevity of sulphur battery Life.
Above content is to combine specific preferred embodiment further description made for the present invention, it is impossible to assert Specific implementation of the invention is confined to these explanations.For general technical staff of the technical field of the invention, On the premise of not departing from present inventive concept, some simple deduction or replace can also be made, should be all considered as belonging to of the invention Protection domain.

Claims (7)

1. a kind of Ti3C2Tx/ KIT-1 types be classified sulphur carbon composite, it is characterised in that by the carbon material of spherical hierarchy, It is dispersed in the Ti in hierarchy carbon material3C2TxWith elemental sulfur composition, classification carbon material is in outer layer to elemental sulfur and Ti3C2TxEnter Row cladding, wherein Ti3C2Tx：Carbon：The mass ratio of sulphur is 0.1-0.3：0.1-0.3:1, classification carbon material is by meso-porous carbon material and outward The micro-pore carbon material composition of the organic carbon of layer cladding.
2. a kind of Ti as claimed in claim 13C2Tx/ KIT-1 types are classified the preparation method of sulphur carbon composite, and its feature exists In, including following steps：
Step（1）：The silsesquioxane of octaphenyl eight is added in 1,2- dichloroethanes, mechanical agitation dissolving is added Ti3AlC2Ceramic powders and KIT-1 powder, stirring form suspension；
Step（2）：To adding anhydrous Aluminum chloride catalyst and carbon tetrachloride to add in suspension, stirring crosslinking reaction 10h reacts After end, ethanol/water solution is added, ethanol/dilute hydrochloric acid solution is washed, washes, is vacuum dried, and obtains presoma；
Step（3）Presoma is placed in the Muffle furnace of nitrogen atmosphere protection, the reaction of 900 DEG C 3h2 °C/min high temperature cabonizations；
Step（4）Product after carbonization is placed in hydrofluoric acid and is performed etching, solution adds deionized water to be centrifuged after corrosion Treatment, then dries sediment, obtains Ti3C2Tx/ spherical porous carbon material；
Step（5）By Ti3C2Tx/ spherical porous carbon material is well mixed with elemental sulfur, is positioned over 155- in the tube furnace of sealing 165 DEG C are reacted 12 hours, are heated to 200 DEG C and are passed through nitrogen reaction 30 minutes, after natural cooling, obtain Ti3C2Tx/ KIT-1 Type is classified sulphur carbon composite.
3. method as claimed in claim 2, it is characterised in that the step（1）The silsesquioxane of middle octaphenyl eight：1,2- bis- The ratio of chloroethanes is 1g：50-100mL, stirring reaction temperature is 50-70 DEG C, the silsesquioxane of octaphenyl eight and Ti3AlC2Pottery The mass ratio of porcelain powder is 1：0.05-0.5, the silsesquioxane of octaphenyl eight is 1 with the mass ratio of KIT-1：0.05-0.5.
4. method as claimed in claim 2, it is characterised in that the step（2）Middle catalyst is anhydrous Aluminum chloride, catalyst Quality be the 5-10% of the silsesquioxane quality of octaphenyl eight, crosslinking agent is carbon tetrachloride, and crosslinking agent quality is the silicon of octaphenyl eight 10-40 times of sesquioxyalkane quality, the stirring reaction time is 5-10 hours, ethanol in ethanol/water solution：The volume ratio of water is 2-4： 1, watery hydrochloric acid is the hydrochloric acid solution that mass fraction is 10%, ethanol and watery hydrochloric acid volume ratio 2-4 in ethanol/dilute hydrochloric acid solution：1.
5. method as claimed in claim 2, it is characterised in that the step（3）Reaction atmosphere in middle Muffle furnace is nitrogen, 800-1200 DEG C of reaction temperature, reaction time 1-5 hours, 1-5 °C/minute of programming rate.
6. method as claimed in claim 2, it is characterised in that the step（4）The concentration of middle hydrofluoric acid is 20%-50%, rotten The time of erosion is 4-24 hours.
7. method as claimed in claim 2, it is characterised in that the step（5）Middle Ti3C2Tx/ spherical porous carbon material and list The mass ratio of matter sulphur is 0.1-0.3：1, initial reaction temperature is 155-165 DEG C in tube furnace, and the reaction time is 10-20 hours, It is 180-200 DEG C to be passed through the reaction temperature after nitrogen, and the reaction time is 10-30 minutes.
CN201710229675.7A 2017-04-10 2017-04-10 A kind of Ti3C2Tx/ KIT-1 type is classified sulphur carbon composite Active CN106876683B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105024054A (en) * 2015-07-11 2015-11-04 中国计量学院 Preparation method for polymer/hollow sulfur composite electrode material
CN105958031A (en) * 2016-06-30 2016-09-21 湖南桑顿新能源有限公司 Sulfur-based cathode composite material and preparation method thereof
CN106450205A (en) * 2016-11-02 2017-02-22 南京工业大学 Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105024054A (en) * 2015-07-11 2015-11-04 中国计量学院 Preparation method for polymer/hollow sulfur composite electrode material
CN105958031A (en) * 2016-06-30 2016-09-21 湖南桑顿新能源有限公司 Sulfur-based cathode composite material and preparation method thereof
CN106450205A (en) * 2016-11-02 2017-02-22 南京工业大学 Two-dimensional transition metal carbide (nitride) and nano sulfur particulate composite as well as preparation and application thereof

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