CN107742707A - A kind of preparation method of nano lanthanum oxide/graphene/sulphur composite - Google Patents
A kind of preparation method of nano lanthanum oxide/graphene/sulphur composite Download PDFInfo
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- CN107742707A CN107742707A CN201710957378.4A CN201710957378A CN107742707A CN 107742707 A CN107742707 A CN 107742707A CN 201710957378 A CN201710957378 A CN 201710957378A CN 107742707 A CN107742707 A CN 107742707A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
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- 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
- H01M4/625—Carbon or graphite
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 is a kind of preparation method of nano lanthanum oxide/graphene/sulphur composite.This method comprises the following steps：Carbon disulfide/sulphur solution is added in graphene oxide/nano lanthanum oxide mixing suspension, then the 24h of hydro-thermal reaction 5 in stainless steel cauldron；Cleaning, vacuum freeze drying, obtain nano lanthanum oxide/graphene/sulphur composite.This method it is innovative graphene oxide is reduced, nano-metal-oxide doping is completed with the step of sulfur loaded solvent thermal reaction one, improve reaction efficiency, preparation technology is simple, overcomes in the prior art the shortcomings that lithium-sulphur cell positive electrode active material utilization rate is low, high rate performance is poor, cycle life is short, reaction efficiency is low, preparation technology is complicated.
Description
Technical field
The present invention relates to lithium sulfur battery anode material preparation field, and in particular to a kind of nano lanthanum oxide/graphene/sulphur is multiple
The preparation method and application of condensation material.
Background technology
Nowadays getting worse the problems such as world environments pollution, greenhouse effects, energy crisis, there is the secondary of high-energy-density
Battery has very important significance for solving the prominent energy and environmental problem.Lithium rechargeable battery has high reversible appearance
The excellent properties such as amount, high voltage, high circulation performance and higher energy density, it is leading power supply practical at present.And traditional lithium
Ion battery positive electrode has relatively low theoretical specific capacity, limits further development such as LiFePO4.And lithium sulphur
Battery typically using elemental sulfur or sulphurous materials as positive active material, its theoretical energy density reach as high as 2600Wh/kg,
Theoretical discharge specific capacity reaches representative and the direction that 1675mAh/g is the secondary cell with high-energy-density.With other battery phases
Than lithium-sulfur cell also has the advantages that Sulphur ressource is abundant, environment-friendly, cheap.
Although lithium-sulfur cell has many advantages, such as, the problem of some are serious is also faced with：1st, elemental sulfur is at room temperature
For electronics and ion insulator；2nd, elemental sulfur can be reduced into readily soluble polysulfide in discharge process, cause active material
It is lost in；3rd, the direct contacting metal cathode of lithium of polysulfide of electrolyte is dissolved in, self discharge reaction occurs；4th, sulphur in charge and discharge process
Corresponding contraction and expansion can occur for electrode, destroy the physical arrangement of electrode to a certain extent.It is resulting to be imitated including shuttling
Various problems including answering, limit the development and commercialization of lithium-sulfur cell.Therefore need to develop to lead with superior structural and height
Electrical positive electrode solves these problems, common are carbon/sulphur composite, conducting polymer/sulphur composite at present
And metal oxide/sulphur composite.For carbon/sulphur composite, it is related to porous carbon/sulphur composite, CNT/sulphur
Composite, carbon nano-fiber/sulphur composite, graphene/sulphur composite, graphite oxide/sulphur composite etc..Its feature
It is that raw material sources are extensive, structure designability is strong.But still need to simplify preparation technology, while improve cyclical stability and forthright again
Energy.Such as CN103199224B reports the preparation method and its application method of a kind of lithium sulfur battery anode material, using improvement
Hummer methods prepare graphite oxide, and sulphur is uniformly mixed with graphite oxide by chemically reacting.Using ascorbic acid as reduction
Agent is reduced to obtain graphene/sulfur composite positive electrode material to the compound of graphite oxide/sulphur.But the patent is only with original position
Composite algorithm makes sulphur and graphene mutually compound, be not significantly improved sulfur electrode the shortcomings that, battery performance is poor.Such as CN
104143630A reports graphene-nano metal oxide composite material and applied in lithium-sulfur cell, using ultraviolet light
Method redox graphene-nano metal oxide composite material suspension, oxygen reduction fossil is obtained by freeze-drying
Black alkene-nano metal oxide composite material, in subsequent tube furnace calcining it is compound to obtain sulphur-graphene-nano-metal-oxide
Material.But the processing step complexity of the preparation from material considers, the standby modified graphene aeroge step for carrying sulphur of the patent system
Rapid complexity, raw material types are more, production cost is higher.
Graphene is a kind of new material for the individual layer laminated structure being made up of carbon atom.Be one kind by carbon atom with sp2It is miscellaneous
Change the flat film that track composition hexangle type is in honeycomb lattice, the two-dimensional material of only one carbon atom thickness.Its electricity under normal temperature
Transport factor is more than 15000cm2/ Vs, in addition it is higher than CNT and silicon crystal, and resistivity about 10-6Ω cm, compare copper
It is the minimum material of resistivity in the world so far or silver is lower.Therefore using redox graphene as lithium-sulfur cell
Positive electrode is advantageous to improve the electric conductivity of positive pole.And this two-dimensional structure of graphene is advantageous to the fixation of more lithium sulfides.Stone
Black this two-dimensional network structure of alkene provides unimpeded transmission channel for electric transmission, but the graphene platelet being layered easily weighs
The new structure for being stacked into multilayer, which results in graphene to lose high-specific surface area and some its intrinsic physical chemistry
Property.The pattern of sulphur and granularity in the composite that active material obtains with graphene after compound is caused to be difficult to control, so as to get
Sulphur positive pole still have very high capacity attenuation in the battery.
The content of the invention
Technical scheme is used by the present invention solves the technical problem：The present invention is directed to lithium-sulphur cell positive electrode active material
A kind of the problem of utilization rate is low, high rate performance is poor and cycle life is short, there is provided nano lanthanum oxide/graphene/sulphur composite
Preparation method.This method it is innovative graphene oxide is reduced, nano-metal-oxide doping it is anti-with sulfur loaded solvent heat
Answer a step to complete, improve reaction efficiency, preparation technology is simple, overcomes lithium-sulphur cell positive electrode active material utilization in the prior art
The shortcomings that rate is low, high rate performance is poor, cycle life is short, reaction efficiency is low, preparation technology is complicated.Obtained simultaneously using this method
Nano lanthanum oxide/graphene/sulphur composite has preferable chemical property in the positive pole for lithium ion battery,
Under 0.1C multiplying powers, the discharge capacity first of the material is up to 1390mAh/g.
The technical solution adopted by the present invention is：
A kind of preparation method of nano lanthanum oxide/graphene/sulphur composite, comprises the following steps：
The first step, nano sulfur powder is dissolved in carbon disulfide, is made into 2-30mg/mL solution；
Second step, graphene oxide, nano lanthanum oxide are added in deionized water, at normal temperatures using ultrasonic disperse instrument
1-3h is disperseed to said mixture ultrasonic wave, obtains graphene oxide/nano lanthanum oxide mixing suspension；
Wherein, quality compares graphene oxide：Nano lanthanum oxide=1:1-20；The quality of graphene oxide and nano lanthanum oxide
Sum：Deionized water=0.001-0.03:1；
3rd step, nano lanthanum oxide/graphene/sulphur composite is prepared using hydro-thermal method：
Carbon disulfide/sulphur solution of above-mentioned configuration is taken to be added to above-mentioned graphene oxide/nano lanthanum oxide mixing suspension
In, 1-3h is stirred under normal temperature, obtains graphene oxide/nano lanthanum oxide/sulphur mixed solution, the mixed solution is loaded into stainless steel
In reactor, the hydro-thermal reaction 5-24h at 100-200 DEG C；Obtained hydrogel deionized water will be reacted at 60-110 DEG C
Cleaning 2-6 times, by obtained product in -45 DEG C of vacuum freeze drying 5-12h, that is, it is compound to obtain nano lanthanum oxide/graphene/sulphur
Material.
Wherein, quality compares graphene oxide：Sulphur=1:1-5；
The power of ultrasonic disperse instrument is 35-60kHz in described second step.
Vacuum drying vacuum in the 3rd described step is 20Pa.
Above-mentioned nano lanthanum oxide/graphene/sulphur composite material and preparation method thereof, wherein involved raw material pass through business
Purchase obtains, and equipment used and technique are known to those skilled in the art.
Compared with prior art, the inventive method has the substantive distinguishing features of protrusion as follows：
In the preparation method of the present invention, nano lanthanum oxide is prepared using the precipitation method, technique is simple, production cost is low, is easy to
Industrialization is realized, and the nano-particle that particle is small, purity is high can be made.Using nano lanthanum oxide to conventional graphite alkene/sulphur
The improvement that the preparation technology and material modification of composite are carried out, effectively prevent the rendezvous problem between graphene sheet layer, has
Effect suppresses the dissolving of polysulfide in the electrolytic solution in charge and discharge process, improves the utilization rate of active sulfur and the electrification of discharge and recharge
Learn performance.
The useful achievement of the present invention：
(1) in the preparation process in accordance with the present invention, nano lanthanum oxide is prepared with graphene by hydro-thermal method three-dimensional netted
Structure, the dissolving of polysulfide can be reduced and improve the load capacity of sulphur, be easy to diffusion and the ion transport of electrolyte, have battery
There is good cyclical stability.
(2) in design process of the invention, nano lanthanum oxide/graphite is prepared by carbon disulfide/sulphur solution dispersion liquid method
Alkene/sulphur composite, it is ensured that nano-sulfur is well-dispersed in graphene network structure, and sulfur content is up in composite
70%, sulphur load capacity in composite, and sulphur Load Balanced are fully improved, effectively improves the electrification of lithium sulfur battery anode material
Learn performance；
(3) positive pole prepared by positive electrode provided by the invention is applied in lithium-sulfur cell, has capacity height, cycle performance
Well, the advantages that raw material sources are extensive, cost is low, green non-pollution.Lithium-sulfur cell electrode material provided by the invention can be notable
" the shuttle effect " of polysulfide is reduced, is effectively improved lithium-sulfur cell cycle performance.Compared with conventional art, discharge capacity significantly increases
Add, and discharge cycle performance is good, under 0.1C power-discharging densities, discharge capacity reaches 1400mAh/g first；
(4) low in raw material price of positive material for lithium-sulfur battery provided by the invention is pollution-free, and preparation technology is simple, relates to
And raw material and equipment cost it is low, there is preferable actual application value, be adapted to large-scale production.
Brief description of the drawings
Fig. 1 is the XRD of nano lanthanum oxide material made from embodiment 1；
Fig. 2 is the thermal multigraph of nano lanthanum oxide/graphene/sulphur composite made from embodiment 1；
Fig. 3 is the charging and discharging curve figure of nano lanthanum oxide/graphene/sulphur composite made from embodiment 1.
Embodiment
Embodiment 1
(1) graphene oxide is prepared using Hummers methods：First by 1g graphite (325 mesh), 0.5gNaNO3It is dense with 23mL
Sulfuric acid is poured into 250mL beakers, is added in above-mentioned beaker 3g KMnO4 under ice bath state, is then stirred 30min, Zhi Hou
30mL deionized waters are added under stirring, continue to stir 15min.Then 50mL deionized waters are added again, are finally being mixed
30ml H are added in solution2O2, graphite oxide solution is obtained (containing a large amount of H+).Gone being added in the graphite oxide solution of preparation
Ionized water, centrifugation (6000 turns/min of rotating speed) in centrifuge tube is placed in, supernatant in centrifuge tube is removed after centrifugation, and add go again
Ionized water, centrifuge (6000 turns/min of rotating speed), repeat this operation, until pH value of solution=7, it is molten to finally give neutral alumina graphite
Liquid.By the graphite oxide solution of preparation, using ultrasonic disperse instrument, ultrasonic wave disperses 2h under 50kHz at normal temperatures, obtains aoxidizing stone
Black alkene solution, it is subsequently placed at 60 DEG C of drying box dry 24h and obtains graphene oxide powder；
(2) solution that a certain amount of lanthanum chloride is made into 0.2mol/L is weighed, NaOH to pH=10 is added dropwise.2h is stood, will be heavy
Form sediment and filter, with water washing is distilled 3 times, be subsequently placed in 90 DEG C of baking oven and dry 6h；Wherein, NaOH molar concentrations are 0.6moL/
L。
(3) dried sediment is ground slightly, or is directly loadable into mortar, is put into tube furnace, in a nitrogen atmosphere,
750 DEG C of calcining 5h, obtain nano lanthanum oxide (particle size range 20-35nm)；
(4) the nano sulfur powder (purity 99.99%) for weighing certain mass is dissolved in carbon disulfide that (purity is
99.5%), it is made into 20mg/mL solution；
(5) according to mass ratio 1:8 ratio weighs the graphene oxide of first step preparation, nano lanthanum oxide, according to mixing
Thing (i.e. nano lanthanum oxide and graphene oxide) is 0.01 with deionized water quality ratio:1 ratio, add mixture to from
In sub- water, at normal temperatures using ultrasonic disperse instrument 65kHz to said mixture ultrasonic wave disperse 1h, obtain graphene oxide/
The uniform mixing suspension of nano lanthanum oxide；
(6) take carbon disulfide/sulphur solution of above-mentioned configuration to be added to above-mentioned graphene oxide/nano lanthanum oxide uniformly to mix
(wherein graphene oxide, sulphur mass ratio are 1 in suspension:1) 1h, is stirred under normal temperature, obtains graphene oxide/nano oxidized
Lanthanum/sulphur mixed solution, the mixed solution is loaded into stainless steel cauldron hydro-thermal reaction 10h at 180 DEG C；
(7) hydrogel that reaction obtains is cleaned 3 times repeatedly with deionized water at 90 DEG C, by obtained product subzero
45 DEG C, vacuum freeze drying 12h under the conditions of vacuum 20Pa, that is, obtain nano lanthanum oxide/graphene/sulphur composite.
Fig. 1 is the X-ray diffractogram of the nano lanthanum oxide material obtained by the present embodiment.It can be seen that diffraction
Collection of illustrative plates does not have miscellaneous peak appearance, and the nano lanthanum oxide sample for illustrating to prepare does not have impurities phase.
Fig. 2 is the thermogravimetric curve figure of nano lanthanum oxide/graphene/sulphur composite obtained by the present embodiment.From figure
As can be seen that in nano lanthanum oxide/graphene/sulphur composite sulphur weight/mass percentage composition about 70%, show the composite
Three-dimensional structure is excellent, there is big specific surface area, is advantageous to the storage of sulphur.
Nano lanthanum oxide/graphene/sulphur the composite prepared by the method for above-described embodiment 1, in lithium-sulphur cell positive electrode
Application in material.Nano lanthanum oxide/graphene/sulphur composite that embodiment 1 is obtained and conductive agent Super P and bonding
Agent Kynoar (PVDF) is with mass ratio 8：1：1, which is fully ground mixing, is made into slurry, and even application is in aluminum foil current collector,
Coating layer thickness is 0.3mm, and 12h is dried at 60 DEG C.Dry positive plate is cut into a diameter of 1.5cm disk, by positive pole
Piece assembles to obtain button chargeable lithium ion battery with lithium cathode sheet.Chemical property analysis (BTS- is carried out to prepared sample
5V5mA, new prestige).
Fig. 3 is the first charge-discharge curve of nano lanthanum oxide/graphene/sulphur composite obtained by the present embodiment.By
The figure is visible, and under 0.1C multiplying powers, the discharge capacity first of the material is up to 1390mAh/g, and battery performance is good.
Embodiment 2
(1) prepare graphene oxide using Hummers methods (with embodiment 1)；
(2) solution that a certain amount of lanthanum chloride is made into 0.2mol/L is weighed, NaOH to pH=10 is added dropwise.4h is stood, will be heavy
Form sediment and filter, with water washing is distilled 4 times, be subsequently placed in 60 DEG C of baking oven and dry 10h；Wherein, NaOH molar concentrations are 0.6moL/
L。
(3) dried sediment is ground slightly, or is directly loadable into mortar, is put into tube furnace, in a nitrogen atmosphere,
450 DEG C of calcining 3h, obtain nano lanthanum oxide；
(4) the nano sulfur powder (purity 99.99%) for weighing certain mass is dissolved in carbon disulfide that (purity is
99.5%), it is made into 30mg/mL solution；
(5) according to mass ratio 1:15 ratio weighs the graphene oxide of first step preparation, nano lanthanum oxide, according to mixing
Thing is 0.01 with deionized water quality ratio:1 ratio, is added mixture in deionized water, at normal temperatures using ultrasound point
Dissipate instrument and 2h is disperseed to said mixture ultrasonic wave in 65kHz, obtain the uniform mixing suspension of graphene oxide/nano lanthanum oxide；
(6) take above-mentioned configuration carbon disulfide/sulphur solution (wherein graphene oxide, sulphur mass ratio be 1:1) it is added to
State in the uniform mixing suspension of graphene oxide/nano lanthanum oxide, 1h is stirred under normal temperature, obtain graphene oxide/nano oxidized
Lanthanum/sulphur mixed solution, the mixed solution is loaded into stainless steel cauldron hydro-thermal reaction 10h at 180 DEG C；
(7) hydrogel that reaction obtains is cleaned 3 times repeatedly with deionized water at 60 DEG C, by obtained product subzero
45 DEG C, vacuum freeze drying 12h under the conditions of vacuum 20Pa, that is, obtain nano lanthanum oxide/graphene/sulphur composite.
Embodiment 3
(1) prepare graphene oxide using Hummers methods (with embodiment 1)；
(2) solution that a certain amount of lanthanum chloride is made into 2mol/L is weighed, NaOH to pH=10 is added dropwise.4h is stood, will be precipitated
Filtering, use, with water washing is distilled 6 times, be subsequently placed in 100 DEG C of baking oven and dry 12h；Wherein, NaOH molar concentrations are
0.6moL/L。
(3) dried sediment is ground slightly, or is directly loadable into mortar, is put into tube furnace, in a nitrogen atmosphere,
900 DEG C of calcining 6h, obtain nano lanthanum oxide；
(4) the nano sulfur powder (purity 99.99%) for weighing certain mass is dissolved in carbon disulfide that (purity is
99.5%), it is made into 30mg/mL solution；
(5) according to mass ratio 1:20 ratio weighs the graphene oxide of first step preparation, nano lanthanum oxide, according to mixing
Thing is 0.01 with deionized water quality ratio:1 ratio, is added mixture in deionized water, at normal temperatures using ultrasound point
Dissipate instrument and 1h is disperseed to said mixture ultrasonic wave in 65kHz, obtain the uniform mixing suspension of graphene oxide/nano lanthanum oxide；
(6) take above-mentioned configuration carbon disulfide/sulphur solution (wherein graphene oxide, sulphur mass ratio be 1:2) it is added to
State in the uniform mixing suspension of graphene oxide/nano lanthanum oxide, 1h is stirred under normal temperature, obtain graphene oxide/nano oxidized
Lanthanum/sulphur mixed solution, the mixed solution is loaded into stainless steel cauldron hydro-thermal reaction 24h at 150 DEG C；
(7) hydrogel that reaction obtains is cleaned 3 times repeatedly with deionized water at 90 DEG C, by obtained product subzero
45 DEG C, vacuum freeze drying 12h under the conditions of vacuum 20Pa, that is, obtain nano lanthanum oxide/graphene/sulphur composite.
Unaccomplished matter of the present invention is known technology.
Claims (3)
- A kind of 1. preparation method of nano lanthanum oxide/graphene/sulphur composite, it is characterized in that this method comprises the following steps：The first step, nano sulfur powder is dissolved in carbon disulfide, is made into 2-30mg/mL solution；Second step, graphene oxide, nano lanthanum oxide are added in deionized water, at normal temperatures using ultrasonic disperse instrument to upper State mixture ultrasonic wave and disperse 1-3h, obtain graphene oxide/nano lanthanum oxide mixing suspension；Wherein, quality compares graphene oxide：Nano lanthanum oxide=1:1-20；The quality sum of graphene oxide and nano lanthanum oxide： Deionized water=0.001-0.03:1；3rd step, nano lanthanum oxide/graphene/sulphur composite is prepared using hydro-thermal method：Carbon disulfide/sulphur solution of above-mentioned configuration is taken to be added in above-mentioned graphene oxide/nano lanthanum oxide mixing suspension, often The lower stirring 1-3h of temperature, obtains graphene oxide/nano lanthanum oxide/sulphur mixed solution, the mixed solution is loaded into stainless steel reaction In kettle, the hydro-thermal reaction 5-24h at 100-200 DEG C；Obtained hydrogel will be reacted to be cleaned at 60-110 DEG C with deionized water 2-6 times, by obtained product in -45 DEG C of vacuum freeze drying 5-12h, that is, obtain nano lanthanum oxide/graphene/sulphur composite wood Material；Wherein, quality compares graphene oxide：Sulphur=1:1-5.
- 2. the preparation method of nano lanthanum oxide/graphene/sulphur composite as claimed in claim 1, it is characterized in that described The power of ultrasonic disperse instrument is 35-60kHz in second step.
- 3. the preparation method of nano lanthanum oxide/graphene/sulphur composite as claimed in claim 1, it is characterized in that described Vacuum drying vacuum in 3rd step is 20Pa.
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Cited By (7)
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| CN108502876A (en) * | 2018-05-08 | 2018-09-07 | 合肥工业大学 | A kind of preparation method of graphene composite Nano lanthana oiliness stable dispersion system |
| CN108693229A (en) * | 2018-05-22 | 2018-10-23 | 上海市农业科学院 | A kind of molecular imprinting electrochemical sensor and preparation method for detecting patulin |
| CN109119616A (en) * | 2018-08-30 | 2019-01-01 | 广东工业大学 | Sulphur/tin oxide/graphene battery positive electrode, preparation method and lithium-sulfur cell |
| CN109167045A (en) * | 2018-09-12 | 2019-01-08 | 肇庆市华师大光电产业研究院 | A method of sulfur-based positive electrode material is prepared using mesh structural porous nano lanthanum oxide |
| CN111342001A (en) * | 2020-03-06 | 2020-06-26 | 上海汽车集团股份有限公司 | Composite sulfur positive electrode for solid-state lithium-sulfur battery, and preparation method and application thereof |
| CN111545211A (en) * | 2020-04-26 | 2020-08-18 | 闽南师范大学 | Graphene oxide-lanthanum oxide-cobalt hydroxide composite material, and synthesis method and application thereof |
| WO2021047354A1 (en) * | 2019-09-12 | 2021-03-18 | 齐鲁工业大学 | Pine branch-shaped samarium oxide-graphene-sulfur gel structure material, preparation method therefor, and application thereof |
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Application publication date: 20180227 Assignee: Heyuan Qiangxin Energy Technology Co.,Ltd. Assignor: SYNERGY INNOVATION INSTITUTE OF GDUT, HEYUAN Contract record no.: X2023980036111 Denomination of invention: A Preparation Method of Nanometer Lanthanum oxide/Graphene/Sulfur Composites Granted publication date: 20200821 License type: Common License Record date: 20230531 |