CN109119616A - Sulphur/tin oxide/graphene battery positive electrode, preparation method and lithium-sulfur cell - Google Patents
Sulphur/tin oxide/graphene battery positive electrode, preparation method and lithium-sulfur cell Download PDFInfo
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Abstract
The present invention relates to technical field of nano material more particularly to a kind of sulphur/tin oxide/graphene battery positive electrode, preparation method and lithium-sulfur cells.The invention discloses a kind of preparation methods of sulphur/tin oxide/graphene battery positive electrode, comprising the following steps: step 1: graphene-tin oxide nano composite material is made by hydro-thermal reaction in nitrogen-doped graphene and tin-salt solution；Step 2: the graphene-tin oxide nano composite material and elemental sulfur being mixed to get mixture, sulphur/tin oxide/graphene battery positive electrode is made by vacuum fusion diffusion reaction in the mixture.The invention also discloses the sulphur/tin oxide/graphene battery positive electrodes and its lithium-sulfur cell that are prepared by the above method.The present invention, which solves elemental sulfur in the prior art, cannot efficiently use in lithium sulfur battery anode material and then cause short lithium-sulfur cell service life, electric conductivity, cyclical stability and the poor technical problem of security performance.
Description
Technical field
The present invention relates to technical field of nano material more particularly to a kind of sulphur/tin oxide/graphene battery positive electrode,
Preparation method and lithium-sulfur cell.
Background technique
It is used to meet increasingly increased extensive energy storage demand and sustainability, develops new electrochemical energy storage
System is extremely urgent.In new energy storage system, compare energy by the theory for the lithium-sulfur cell that cathode, elemental sulfur are anode of lithium metal
Amount can reach 2600Wh/kg (theoretical specific capacity of lithium and sulphur is respectively 3860mAh/g and 1675mAh/g), much larger than at this stage
Used commercialization secondary cell.In addition, lithium-sulfur cell is because of the low, environment with high-energy-density advantage outstanding and cost of material
The advantages that friendly and receive significant attention, therefore be considered as the research direction of most worthy in next-generation large-scale energy storage system
One of.
However, the commercialization of lithium-sulfur cell still encounters some technical obstructions, such as since sulphur simple substance can not have
Effect fixation causes the utilization rate of positive active material sulphur not high, in addition, shuttle effect and lithium sulphur that polysulfide dissolution generates
The utilization rate that the change of battery volume will lead to sulphur simple substance is fallen, so that the cyclical stability of lithium-sulfur cell is deteriorated, or even also
A series of safety problem can be generated.
Fixation for lithium-sulfur cell elemental sulfur, the current general carrying capacity of load sulphur method is not high or complex steps, such as
Using continuous carbon coating and solution phase oxidation reaction method, carbon packet sulphur nanometer sheet is synthesized, when preparing pure zinc sulphide nanometer sheet
Zinc sulphide hybridized nanometer piece need to be calcined under high temperature inert environment.This method there are certain requirements equipment, and step is numerous
It is trivial to be not suitable for being mass produced, in addition, mixing sublimed sulfur with mesopore silicon oxide there are also method, by secondary clacining, pass through hair
Sulphur simple substance is embedded in aperture by tubule power, obtains silica sulfur compound.This method completes solid sulphur by capillary force, securely
Property is still barely satisfactory.
Therefore, since sulphur simple substance stationarity is poor, polysulfide dissolution generates in existing lithium sulfur battery anode material
The change of shuttle effect and lithium-sulfur cell volume so cause short lithium-sulfur cell service life, electric conductivity, cyclical stability and
Security performance is poor to become those skilled in the art's technical problem urgently to be resolved.
Summary of the invention
In view of this, the present invention provides a kind of sulphur/tin oxide/graphene battery positive electrode, preparation method and lithium sulphur
Battery, in the prior art since sulphur simple substance stationarity is poor, the shuttle effect and lithium-sulfur cell body of polysulfide dissolution generation
Long-pending change and then lead to short lithium-sulfur cell service life, electric conductivity, cyclical stability and the poor technical problem of security performance.
The present invention provides a kind of preparation methods of sulphur/tin oxide/graphene battery positive electrode, comprising the following steps:
Step 1: graphene-tin oxide nano composite wood is made by hydro-thermal reaction in nitrogen-doped graphene and tin-salt solution
Material；
Step 2: the graphene-tin oxide nano composite material and elemental sulfur are mixed to get mixture, it will be described mixed
It closes object and sulphur/tin oxide/graphene battery positive electrode is made by vacuum fusion diffusion reaction.
It is furthermore preferred that before step 1 further including that graphene oxide and nitrogen source are passed through Hummers at 80~100 DEG C
Method reacts 10~30h, and nitrogen-doped graphene is made.
Further preferably, the reaction temperature of the Hummers method is 80 DEG C or 90 DEG C
Further preferably, the reaction time of the Hummers method is for 24 hours or 30h.
It is furthermore preferred that the nitrogen source includes one kind or any two of cyanamide, melamine, cyanamid dimerization and aryl cyanamide
Kind.
Further preferably, the nitrogen source includes melamine, cyanamide or cyanamid dimerization.
Preferably, the temperature of the hydro-thermal reaction is 100~130 DEG C.
It is furthermore preferred that the temperature of the hydro-thermal reaction is 100 DEG C, 120 DEG C or 130 DEG C.
Preferably, the time of the hydro-thermal reaction is 0.5~4h.
It is furthermore preferred that the time of the hydro-thermal reaction is 0.5h, 2h, 3h or 4h.
Preferably, the solute of the tin-salt solution includes stannous chloride, tin tetrachloride, nitric acid tin, nitric acid stannous and sulfuric acid
One or both of tin.
It is furthermore preferred that the solute of the tin-salt solution is tin tetrachloride, stannous chloride or nitric acid tin.
Preferably, the ratio of the solute of the tin-salt solution and the nitrogen-doped graphene is 0.002~0.04:1mol/g.
It is furthermore preferred that the solvent of the tin-salt solution is one in carbon tetrachloride, carbon disulfide, dehydrated alcohol and ethylene glycol
Kind is a variety of.
Further preferably, the solvent of the tin-salt solution is dehydrated alcohol, ethylene glycol or carbon tetrachloride.
Preferably, the content of element sulphur is 50%~90% in the mixture.
It is furthermore preferred that the content of element sulphur is 50%, 60%, 70% or 90% in the mixture.
Preferably, the temperature of the vacuum fusion diffusion reaction is 120~180 DEG C.
It is furthermore preferred that the temperature of the vacuum fusion diffusion reaction is 120 DEG C, 140 DEG C, 150 DEG C or 180 DEG C.
Preferably, the time of the vacuum fusion diffusion reaction be 0.5~for 24 hours.
It is furthermore preferred that the time of the vacuum fusion diffusion reaction is for 0.5h, 10h, 12h or for 24 hours.
The present invention also provides a kind of sulphur/tin oxide/graphene battery positive electrodes, by above-mentioned sulphur/tin oxide/graphite
The preparation method of alkene cell positive material is made.
The present invention also provides a kind of lithium-sulfur cell, cathode is lithium-sulfur cell negative electrode material, and anode includes above-mentioned
Sulphur/tin oxide/graphene battery positive electrode.
Sulphur/tin oxide/graphene battery positive electrode that the present invention is prepared, wherein nitrogen-doped graphene has superelevation
Specific surface area and a large amount of active site, can be improved the load capacity of sulphur, further increase in positive electrode the content of sulphur and just
The electric conductivity of pole material.Nitrogen-doped graphene and tin-salt solution by hydro-thermal method, are made the table of nitrogen-doped graphene by the present invention
It face can be with uniform load nano-metal-oxide, that is, tin oxide.Nanoscale granules of stannic oxide size is small, and surface can be big, Ke Yiyou
It imitates fixed elemental sulfur and significantly reduces tin oxide in addition, the present invention passes through the effect of hydro-thermal reaction and nitrogen-doped graphene
Granular size, a large amount of nitrogen-atoms in nitrogen-doped graphene surface can occur coordination with tin atom, keep tin ion uniform
Absorption makes tin ion hydrolysis generate stannic hydroxide on the surface of graphene, by the way that deionized water is added, and makes hydrogen at a proper temperature
Tin oxide, which decomposes, generates tin oxide, and hydrolysis, decomposition are reaction in-situ, not easy to reunite in the process, growth, so can be in graphene
Area load Nano granules of stannic oxide.Granules of stannic oxide is smaller, and surface can be bigger, allows to inhale by stronger chemical action
Attached sulphur and polysulfide reduce the content of high-sulfur compound in electrolyte, not only increase transformation efficiency, also pass through the more vulcanizations of absorption
Object has buffered the volume change of positive electrode, keeps the electrode structure of conducting matrix grain and active material, improve capacity stability and
Service life, to be greatly improved the chemical property of lithium-sulfur cell.
The embodiment of the present invention obtains the stone for having a large amount of active sites by reacting in graphene oxide with nitrogenous substance
Black alkene improves the load sulfur content of nitrogen-doped graphene, in addition, the embodiment of the present invention, which successfully prepares load, granules of stannic oxide
Nitrogen-doped graphene, tin oxide can adsorb polysulfide, inhibit the dissolution of polysulfide, to further promote lithium-sulfur cell
Chemical property.The embodiment of the present invention is uniform on the nitrogen-doped graphene surface with active site by using hydro-thermal reaction
Particle size is loaded in the tin oxide of 2.0~4.0nm, reduces the formation of polysulfide, improves transformation efficiency, and then greatly
Improve the chemical property of lithium-sulfur cell.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is the XPS figure of nitrogen-doped graphene in the embodiment of the present invention 1；
Fig. 2 is graphene-tin oxide nano composite material XRD diagram in the embodiment of the present invention 1；
Fig. 3 is sulphur/tin oxide/graphene battery positive electrode XRD diagram prepared by the embodiment of the present invention 1；
Fig. 4 is sulphur/tin oxide/graphene battery positive electrode TEM figure prepared by the embodiment of the present invention 1；
Fig. 5 is sulphur/tin oxide/graphene battery positive electrode CV figure prepared by the embodiment of the present invention 1.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
It is existing the present invention provides a kind of sulphur/tin oxide/graphene battery positive electrode, preparation method and lithium-sulfur cell
In technology due to sulphur simple substance stationarity is poor, polysulfide dissolution generate shuttle effect and lithium-sulfur cell volume change into
And lead to short lithium-sulfur cell service life, electric conductivity, cyclical stability and the poor technical problem of security performance.
In order to which the present invention is described in more detail, below with reference to embodiment to a kind of sulphur/tin oxide/graphene provided by the invention
Cell positive material, preparation method and lithium-sulfur cell, are specifically described.
Embodiment 1
It prepares nitrogen-doped graphene: measuring the beaker that 150ml 0.8mg/ml graphene oxide water solution is placed in 250ml
In, the cyanamide aqueous solution of 6ml 50wt% is added, stirs evenly, is transferred in three-neck flask, 80 DEG C of reaction 30h will be anti-
It answers product to filter, be washed with deionized, freeze, be freeze-dried, obtains nitrogen-doped graphene.
It prepares graphene-tin oxide nano composite material: weighing 40mg nitrogen-doped graphene, be added to the anhydrous of 200ml
EtOH Sonicate dispersion, then take the tin tetrachloride (SnCl of 0.1mmol4), it is dissolved in the dehydrated alcohol of 10ml, is added to scattered
Nitrogen-doped graphene solution in, magnetic agitation is evenly dispersed to its, then instills the deionized water of 5ml and be transferred to dispersion liquid
100 DEG C of reaction 4h in reaction kettle are filtered, are washed, being freezed, are freeze-dried to get graphite is arrived to reaction product natural cooling
Alkene-tin oxide nano composite material.
Prepare sulphur/tin oxide/graphene battery positive electrode: weigh 30mg graphene-tin oxide nano composite material with
The mixing of 70mg sublimed sulfur is transferred to seal pipe after being fully ground, is filled with so that the content of element sulphur is 70% in said mixture
Inert gas, 120 DEG C reaction for 24 hours to get arrive sulphur/tin oxide/graphene battery positive electrode.
Sulphur/tin oxide/graphene battery positive electrode obtained is tested for the property, Fig. 1 is N doping in embodiment 1
The XPS spectrum figure of graphene, by Fig. 1 and table 1 it is found that the mass percentage content of nitrogen is 23.0% in nitrogen-doped graphene.
The mass percentage of each element in 1 nitrogen-doped graphene of table
Fig. 2 is graphene-tin oxide nano composite material XRD diagram in embodiment 1, as shown in Figure 2, final gained sample
In metal oxide particle be granules of stannic oxide.
Fig. 3 is sulphur/tin oxide/graphene battery positive electrode XRD diagram prepared by embodiment 1, from the figure 3, it may be seen that utilizing
The content that vacuum fusion method mixes sulphur in the sample after sulphur is higher.
Fig. 4 is sulphur/tin oxide/graphene battery positive electrode TEM figure prepared by embodiment 1, as shown in Figure 4, oxidation
Tin particles are evenly distributed in nitrogen-doped graphene surface, and the average particle size particle size of granules of stannic oxide is about 4nm.
Fig. 5 is sulphur/tin oxide/graphene battery positive electrode CV figure prepared by embodiment 1, as shown in Figure 5, sulphur/oxygen
It is preferable to change tin/grapheme material chemical property.
Embodiment 2
Prepare nitrogen-doped graphene: the graphene oxide for weighing 120mg is placed in the beaker of 250ml, and 200ml is added and goes
Ionized water, ultrasonic disperse is uniform, is transferred to three-neck flask.Then the melamine for adding 5g, stirs evenly, 100 DEG C of reactions
Reaction product is filtered, be washed with deionized, freezed by 10h, and freeze-drying obtains nitrogen-doped graphene.
It prepares graphene-tin oxide nano composite material: weighing 40mg nitrogen-doped graphene, ultrasonic disperse is to 160ml's
Ethylene glycol, then take the SnCl of 1mmol4, it is dissolved in the ethylene glycol of 10ml, is then added to scattered nitrogen-doped graphene solution
In, magnetic agitation is evenly dispersed to its, then instills the deionized water of 10ml and dispersion liquid is transferred to 130 DEG C of reactions in reaction kettle
0.5h is filtered, is washed, being freezed, is freeze-dried to get multiple to graphene-tin oxide nano to reaction product natural cooling
Condensation material.
Prepare sulphur/tin oxide/graphene battery positive electrode: weigh 40mg graphene-tin oxide nano composite material with
The mixing of 60mg sublimed sulfur is transferred to seal pipe after being fully ground, is filled with so that the content of element sulphur is 60% in said mixture
Inert gas, reaction 0.5h is to get arriving sulphur/tin oxide/graphene battery positive electrode at 180 DEG C.
Embodiment 3
Prepare nitrogen-doped graphene: the graphene oxide for weighing 120mg is placed in the conical beaker of 250ml, is added
200ml deionized water, ultrasonic disperse are uniform.The cyanamid dimerization for adding 7g later, stirs evenly, 100 DEG C of reaction 16h, will be anti-
Product is answered to filter, deionized water washing, freezing, freeze-drying obtains nitrogen-doped graphene.
It prepares graphene-tin oxide nano composite material: weighing 40mg nitrogen-doped graphene ultrasonic disperse to the four of 200ml
In chlorination carbon, then take the stannous chloride (SnCl of 0.4mmol2), it is dissolved in the carbon tetrachloride of 10ml, is then added to scattered nitrogen
In doped graphene solution, magnetic agitation is evenly dispersed to its, then the deionized water of 8ml is slowly added to, then dispersion liquid is turned
130 DEG C of reaction 3h in reaction kettle are moved on to, to reaction product natural cooling, then filtered, wash, freeze, be freeze-dried 10h,
Obtain graphene-tin oxide nano composite material.
Prepare sulphur/tin oxide/graphene battery positive electrode: weigh 50mg graphene-tin oxide nano composite material with
The mixing of 50mg sublimed sulfur is transferred to seal pipe after being fully ground, is filled with so that the content of element sulphur is 50% in said mixture
Inert gas, reaction 12h is to get arriving sulphur/tin oxide/graphene battery positive electrode at 140 DEG C.
Embodiment 4
Prepare nitrogen-doped graphene: the graphene oxide for weighing 100mg is placed in the beaker of 250ml, and 200ml is added and goes
Ionized water, ultrasonic disperse are uniform.The cyanamide for adding 8ml 50wt% later, stirs evenly, and 90 DEG C of reactions for 24 hours, will react
Product filters, deionized water washing, freezes 12h, and freeze-drying obtains nitrogen-doped graphene.
Prepare graphene-tin oxide nano composite material: weigh 30mg nitrogen-doped graphene ultrasonic disperse to 160ml nothing
In water-ethanol, then take the nitric acid stannous (Sn (NO of 0.9mmol3)2), it is dissolved in the dehydrated alcohol of 8ml, is then added to scattered
In nitrogen-doped graphene solution, magnetic agitation is evenly dispersed to its, then the deionized water of 4ml is slowly dropped into, then by dispersion liquid
Be transferred to 120 DEG C of reaction 2h in reaction kettle, to reaction product natural cooling, then filtered, washed, freeze 12h, -50 DEG C it is cold
Dry 18h is lyophilized to get graphene-tin oxide nano composite material is arrived.
It prepares sulphur/tin oxide/graphene battery positive electrode: weighing 40mg tin oxide/nitrogen-doped graphene and 60mg liter
Magnificent sulphur mixing is transferred to seal pipe after being fully ground, is filled with indifferent gas so that the content of element sulphur is 60% in said mixture
Body, 150 DEG C of reaction 10h to get arrive sulphur/tin oxide/graphene battery positive electrode.
Embodiment 5
Prepare nitrogen-doped graphene: the graphene oxide for weighing 100mg is placed in the beaker of 250ml, and 200ml is added and goes
Ionized water, ultrasonic disperse are uniform.The cyanamide for then adding 8ml 50wt%, stirs evenly, and 80 DEG C of reaction 30h will react
Product filters, deionized water washing, freezes 12h, and freeze-drying obtains nitrogen-doped graphene.
Prepare graphene-tin oxide nano composite material: weigh 30mg nitrogen-doped graphene ultrasonic disperse to 160ml nothing
In water-ethanol, then take the Sn (NO of 1.2mmol3)2, it is dissolved in the dehydrated alcohol of 10ml, is then added to scattered N doping graphite
In alkene solution, magnetic agitation is evenly dispersed to its, then the deionized water of 4ml is slowly dropped into, then dispersion liquid is transferred to reaction
100 DEG C of reaction 4h in kettle to reaction product natural cooling, then are filtered, are washed, freezing 12h, -50 DEG C of freeze-drying 18h,
Obtain graphene-tin oxide nano composite material.
Prepare sulphur/tin oxide/graphene battery positive electrode: weigh 10m graphene-tin oxide nano composite material with
The mixing of 90mg sublimed sulfur is transferred to seal pipe after being fully ground, is filled with so that the content of element sulphur is 90% in said mixture
Inert gas, 180 DEG C of reaction 0.5h to get arrive sulphur/tin oxide/graphene battery positive electrode.
Embodiment 6
Prepare nitrogen-doped graphene: the graphene oxide for weighing 100mg is placed in the beaker of 250ml, and 200ml is added and goes
Ionized water, ultrasonic disperse are uniform.The cyanamide for then adding 8ml 50wt%, stirs evenly, and 90 DEG C of reactions for 24 hours, will react
Product is filtered, deionized water washing, is freezed, and freeze-drying obtains nitrogen-doped graphene.
It prepares sulphur/nitrogen-doped graphene cell positive material: weighing 40mg tin oxide/nitrogen-doped graphene and 60mg distils
Sulphur mixing is transferred to seal pipe after being fully ground, is filled with indifferent gas so that the content of element sulphur is 60% in said mixture
Body, 155 DEG C of reaction 10h to get arrive sulphur/nitrogen-doped graphene cell positive material.
It is observed that after sublimed sulfur and nitrogen-doped graphene vacuum fusion diffusion reaction, it can be seen that apparent Sulfur releasing, through surveying
It tries, sulfur content only has 30% or so in specimen material.,
In conclusion table 1 is sulphur/tin oxide/graphene battery positive electrode results of property made from Examples 1 to 5,
It should be noted that when preparing nitrogen-doped graphene, the nitrogen-atoms being introduced into can replace the oxygen in partial oxidation of graphite alkene, nitrogen with
Key between graphene participates in the reaction of next step, therefore by the content of nitrogen in measurement nitrogen-doped graphene it can be concluded that nitrogen is mixed
The active site content of miscellaneous graphene.
Sulphur/tin oxide/graphene battery positive electrode results of property made from 2 Examples 1 to 5 of table
As shown in Table 2, the embodiment of the present invention 1~5 makes the oxidation on nitrogen-doped graphene surface by using hydro-thermal reaction
Tin particles partial size is smaller, and partial size is smaller, and surface can be bigger, it is made not only can to adsorb sulphur and polysulfide by chemical action,
And intermediate product polysulfide can be catalyzed and be converted into protosulphide, the content of high-sulfur compound in electrolyte is reduced, improves and turns
Change efficiency, to be greatly improved the chemical property of lithium-sulfur cell.In addition, the N doping in the embodiment of the present invention 1~5 is living
Property site content is higher, the load sulfur content of nitrogen-doped graphene can be effectively improved, to further increase the electrical property of lithium-sulfur cell
Energy.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of sulphur/tin oxide/graphene battery positive electrode, which comprises the following steps:
Step 1: graphene-tin oxide nano composite material is made by hydro-thermal reaction in nitrogen-doped graphene and tin-salt solution；
Step 2: the graphene-tin oxide nano composite material and elemental sulfur being mixed to get mixture, by the mixture
Sulphur/tin oxide/graphene battery positive electrode is made by vacuum fusion diffusion reaction.
2. the preparation method of sulphur/tin oxide/graphene battery positive electrode according to claim 1, which is characterized in that institute
The temperature for stating hydro-thermal reaction is 100~130 DEG C.
3. the preparation method of sulphur/tin oxide/graphene battery positive electrode according to claim 1, which is characterized in that institute
The time for stating hydro-thermal reaction is 0.5~4h.
4. the preparation method of sulphur/tin oxide/graphene battery positive electrode according to claim 1, which is characterized in that institute
The solute for stating tin-salt solution includes one or both of stannous chloride, tin tetrachloride, nitric acid tin, nitric acid stannous and STANNOUS SULPHATE CRYSTALLINE.
5. the preparation method of sulphur/tin oxide/graphene battery positive electrode according to claim 4, which is characterized in that institute
The ratio of the solute and the nitrogen-doped graphene of stating tin-salt solution is 0.002~0.04:1mol/g.
6. the preparation method of sulphur/tin oxide/graphene battery positive electrode according to claim 1, which is characterized in that institute
The content for stating element sulphur in mixture is 50%~90%.
7. the preparation method of sulphur/tin oxide/graphene battery positive electrode according to claim 1, which is characterized in that institute
The temperature for stating vacuum fusion diffusion reaction is 120~180 DEG C.
8. the preparation method of sulphur/tin oxide/graphene battery positive electrode according to claim 1, which is characterized in that institute
State vacuum fusion diffusion reaction time be 0.5~for 24 hours.
9. a kind of sulphur/tin oxide/graphene battery positive electrode, which is characterized in that as described in claim 1~8 any one
Sulphur/tin oxide/graphene battery positive electrode preparation method be made.
10. a kind of lithium-sulfur cell, which is characterized in that its cathode is lithium-sulfur cell negative electrode material, and anode includes claim 9 institute
Sulphur/tin oxide/graphene battery the positive electrode stated.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830674A (en) * | 2019-03-29 | 2019-05-31 | 哈尔滨理工大学 | A kind of tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material and the preparation method and application thereof |
| CN110660977A (en) * | 2019-08-23 | 2020-01-07 | 太原理工大学 | Lithium-sulfur electrochemical energy storage system and preparation method thereof |
| CN111192997A (en) * | 2020-01-07 | 2020-05-22 | 北京理工大学 | Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof |
| CN111354933A (en) * | 2020-03-11 | 2020-06-30 | 肇庆市华师大光电产业研究院 | Preparation method of tungsten nitride/nitrogen-doped graphene/tungsten oxide composite material applied to lithium-sulfur battery cathode material |
| CN113422056A (en) * | 2021-06-03 | 2021-09-21 | 江苏智泰新能源科技有限公司 | Composite positive electrode material with array structure and application |
| CN114426301A (en) * | 2020-10-29 | 2022-05-03 | 北京小米移动软件有限公司 | Tin oxide/sulfur-doped graphene composite material, preparation method thereof and battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326007A (en) * | 2013-06-25 | 2013-09-25 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based stannic oxide composite material |
| CN106159228A (en) * | 2016-07-26 | 2016-11-23 | 广东工业大学 | A kind of nitrogen-doped graphene metal oxide nano composite material and its preparation method and application |
| CN106941161A (en) * | 2017-04-05 | 2017-07-11 | 深圳市佩成科技有限责任公司 | A kind of preparation method of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite |
| CN107742707A (en) * | 2017-10-16 | 2018-02-27 | 河源广工大协同创新研究院 | A kind of preparation method of nano lanthanum oxide/graphene/sulphur composite |
| CN108011085A (en) * | 2017-11-29 | 2018-05-08 | 北京师范大学 | A kind of lithium sulfur battery anode material, its preparation method and its application |
-
2018
- 2018-08-30 CN CN201811004064.3A patent/CN109119616A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326007A (en) * | 2013-06-25 | 2013-09-25 | 上海交通大学 | Preparation method and application of three-dimensional graphene-based stannic oxide composite material |
| CN106159228A (en) * | 2016-07-26 | 2016-11-23 | 广东工业大学 | A kind of nitrogen-doped graphene metal oxide nano composite material and its preparation method and application |
| CN106941161A (en) * | 2017-04-05 | 2017-07-11 | 深圳市佩成科技有限责任公司 | A kind of preparation method of nitrogen-doped graphene/manganese dioxide/hollow sulphur composite |
| CN107742707A (en) * | 2017-10-16 | 2018-02-27 | 河源广工大协同创新研究院 | A kind of preparation method of nano lanthanum oxide/graphene/sulphur composite |
| CN108011085A (en) * | 2017-11-29 | 2018-05-08 | 北京师范大学 | A kind of lithium sulfur battery anode material, its preparation method and its application |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830674A (en) * | 2019-03-29 | 2019-05-31 | 哈尔滨理工大学 | A kind of tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material and the preparation method and application thereof |
| CN109830674B (en) * | 2019-03-29 | 2022-01-11 | 哈尔滨理工大学 | Tin oxide/carbonized aerogel core-shell structure composite sulfur electrode material and preparation method and application thereof |
| CN110660977A (en) * | 2019-08-23 | 2020-01-07 | 太原理工大学 | Lithium-sulfur electrochemical energy storage system and preparation method thereof |
| CN111192997A (en) * | 2020-01-07 | 2020-05-22 | 北京理工大学 | Diaphragm for activated carbon-loaded tin oxide lithium-sulfur battery and preparation method and application thereof |
| CN111354933A (en) * | 2020-03-11 | 2020-06-30 | 肇庆市华师大光电产业研究院 | Preparation method of tungsten nitride/nitrogen-doped graphene/tungsten oxide composite material applied to lithium-sulfur battery cathode material |
| CN111354933B (en) * | 2020-03-11 | 2022-06-17 | 肇庆市华师大光电产业研究院 | Preparation method of tungsten nitride/nitrogen-doped graphene/tungsten oxide composite material applied to lithium-sulfur battery cathode material |
| CN114426301A (en) * | 2020-10-29 | 2022-05-03 | 北京小米移动软件有限公司 | Tin oxide/sulfur-doped graphene composite material, preparation method thereof and battery |
| CN113422056A (en) * | 2021-06-03 | 2021-09-21 | 江苏智泰新能源科技有限公司 | Composite positive electrode material with array structure and application |
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