CN104617283B - The preparation method of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode and the preparation method of positive pole - Google Patents
The preparation method of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode and the preparation method of positive pole Download PDFInfo
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Abstract
The preparation method of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme sulphur positive electrode and the preparation method of positive pole, it relates to preparation method and the preparation method of positive pole of lithium sulfur battery anode material.The present invention is to solve the technical problem that area ratio capacity is low, high rate performance is poor of existing Graphene sulfur electrode.The positive electrode of the present invention is among the hole that elemental sulfur is dispersed within carbon fiber modifying spongy graphene.Preparation method: carbon fiber joins the mixed liquor of graphene oxide dispersion, obtains hydrogel, freeze-drying after Hydrothermal Synthesis, obtain carbon fiber modifying three-dimensional sponge shape Graphene；It is cut into thin slice, and elemental sulfur is sprinkled upon sheet surface, put in vacuum tank, after heating, obtain lithium-sulfur cell fibre reinforced three-dimensional grapheme sulphur positive electrode.After positive electrode is cut into slices, compacting, obtain positive pole.The area ratio capacity of this electrode material reaches 10mAh/cm2, can be used in lithium ion battery.
Description
Technical field
The present invention relates to the preparation method of lithium sulfur battery anode material and the preparation method of positive pole.
Background technology
In recent years, along with the continuous progress of science and technology, the fast development of various electronic products, it is desirable to electrochmical power source used has
The features such as light weight, volume are little, capacity is big.The specific energy of the commercial lithium-ion batteries being currently based on lithium intercalation/deintercalation is subject to
The restriction of its positive electrode theoretical specific capacity, such as LiCoO2Theoretical specific capacity be 274mAh/g, in order to maintain charge and discharge
The invertibity of electricity circulation and security, the lithium of deintercalation half during actual charging.Therefore, current lithium ion battery specific energy
It is difficult to more than 200Wh/kg.Going no further of positive electrode becomes the bottleneck that limiting lithium ion cell specific capacity improves, because of
This needs a kind of novel lithium battery positive electrode with more high-energy-density of exploitation badly.
Lithium-sulfur cell is as the high power capacity energy storage system of a kind of novel great development prospect, and theoretical specific energy is up to 2600
Wh/kg, and stability, security and on the life-span outstanding.Additionally, compared to the transition gold of commercialization the most
Belonging to oxide anode material, Sulphur ressource is abundant, ($ 150 is per ton) with low cost, the feature such as environmental friendliness also make it have rule
The value of modelling application.Lithium-sulfur cell have the advantage that makes it be acknowledged as the most promising energy storage device of future generation, becomes
The focus of countries in the world research.But, lithium-sulfur cell, while there is above advantage, there is also a series of shortcoming, limit
Make the development of lithium-sulfur cell.Specifically include that (1) elemental sulfur electronics at room temperature and ion insulator, its electronic conduction
Rate is only 5 × 10-30S/cm, it is impossible to separately as positive pole；(2) due to the Li of active material S with electric discharge end product2S
Density different, in discharge and recharge course of reaction, especially under big multiplying power, cause the Volume Changes of positive electrode, produce internal
Stress, destroys electrode structure, easily causes electrode material and cave in, affect the cycle life of battery；(3) charge and discharge process is sent out
Raw effect of shuttling back and forth, effect of shuttling back and forth refers to the sulphur intermediate product polysulfide (Li at electrochemical reduction2Sx, 4≤x≤8) readily soluble
Solution, in organic electrolyte, causes the loss of active material, and the polysulfide being dissolved in electrolyte is between battery plus-negative plate
Shuttle back and forth reciprocal, cause the irreversible loss of active material, and significantly reduce efficiency for charge-discharge, when polysulfide spreads
To negative pole, react with cathode of lithium, cause self-discharge of battery, and react the Li generating solid isolation2S and Li2S2,
Cause the irreversible loss of cathode of lithium surface deterioration and active material, additionally, the end product (Li of sulphur electrochemical reduction2S
And Li2S2) it is insoluble megohmite insulant, easily block electronics and the ion transmission channel of sulphur positive pole.Problems above will be made
The specific capacity becoming lithium-sulfur cell reduces and cycle life shortens.
At present, people, in order to improve the specific capacity of lithium-sulfur cell, improve its cycle performance, have carried out the most many trials,
Use material with carbon element, conducting polymer materials and oxide etc. to modify sulphur positive pole, but great majority research all concentrates on and improves sulphur
Specific discharge capacity, for elemental sulfur, under 0.1C charge-discharge magnification, its capacity is up to more than 1000mAh/g.To the greatest extent
Pipe so, still go no further by the application of lithium-sulfur cell, and the surface density mainly due to the electrode material of research employing is the least
In 2mg/cm2, it is far smaller than current lithium ion battery and uses surface density (the about 20mg/cm of electrode2), cause electrode material
Area ratio capacity reduce, thus greatly reduce the actual specific capacity of battery.It is thus desirable to use a kind of new electrode to carry
The area ratio capacity of high electrode material, thus improve the actual specific capacity of battery.
Cheng huiming et al. discloses one in volume 7 the 6th phases page 5367～5375 in 2013 of " nano material "
Plant and use poisonous CS2For raw material, the three-dimensional sponge shape graphene-sulfur electrode prepared by hydro-thermal method, but the electricity of preparation
The surface density of pole only has 2mg/cm2, and high rate performance is poor.
Summary of the invention
The present invention is to solve the technical problem that area ratio capacity is low, high rate performance is poor of existing graphene-sulfur electrode, and
Preparation method and the preparation method of positive pole of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive pole are provided.
One lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode of the present invention is that elemental sulfur is dispersed in carbon fiber modifying
Among hole within spongy graphene, wherein in positive electrode, the mass percent of elemental sulfur is 40%～85%, and carbon is fine
The mass percent of dimension is 2%～8%, and the mass percent of Graphene is 7%～58%.
The preparation method of above-mentioned a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode, enters according to the following steps
OK:
One, weigh carbon fiber, Graphene and elemental sulfur respectively, the quality summation of carbon fiber, Graphene and elemental sulfur is calculated as
M, wherein the quality of elemental sulfur accounts for the 40%～85% of M, and the quality of the quality of carbon fiber accounts for the 2%～8% of M, Graphene
Quality account for the 7%～58% of M；After first Graphene being aoxidized, it is added to the water and stirs, obtain graphene oxide and divide
Dissipate liquid；Again carbon fiber is joined in graphene oxide dispersion, stirring, obtain mixed liquor；Wherein graphene oxide dispersion
The concentration of middle graphene oxide is 3.0～5.0mg/ml；
Two, mixed liquor is transferred in water heating kettle, under conditions of temperature is 180～200 DEG C after hydro-thermal reaction 18～20h,
Obtain carbon fiber modifying three-dimensional sponge shape Graphene hydrogel；Again carbon fiber modifying three-dimensional sponge shape Graphene hydrogel is carried out
Freeze-drying, obtains carbon fiber modifying three-dimensional sponge shape Graphene；
Three, carbon fiber modifying three-dimensional sponge shape Graphene is thinly sliced, and elemental sulfur is sprinkled upon equably sheet surface, put
Enter in vacuum tank, be 10 in vacuum-5～be heated to 155～160 DEG C under conditions of 1kPa and keep 2～5h, obtain lithium sulphur electricity
Pond fibre reinforced three-dimensional grapheme-sulphur positive electrode.
The method utilizing above-mentioned a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode to prepare positive pole is: will
After lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode is cut into sheet, the pressure with 2～10MPa is suppressed, and obtains
Thickness is the carbon fiber modifying spongy graphene-sulfur electrode positive pole of 100～300 microns.
One carbon fiber modifying spongy graphene-sulfur electrode material of the present invention is sintered by carbon fiber modifying Graphene and elemental sulfur
Forming, in lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode, three-dimensional grapheme not only produces in the middle of discharge and recharge
The effect that thing effectively adsorbs, also acts as coating function, it is often more important that, due to the addition of carbon fiber, it is suppressed that sulphur
Reunite, it is to avoid form big sulfur granules, extenuated the stress that Volume Changes is brought, shorten the transmission of electronics and lithium ion
Path, improves the electric conductivity of electrode, improves high rate performance and the cycle life of battery.Meanwhile, the addition of carbon fiber,
Be conducive to improving the mechanical performance of electrode, provide stability support to electrode Volume Changes in charge and discharge process, improve sulphur
Base composite active material charge-discharge performance.And preparation process asepsis environment-protecting.
Carbon fiber modifying spongy graphene-sulfur electrode material prepared by the present invention has self supporting structure, it is to avoid metal collection
Stream device and the use of binding agent, reduce cost, further increase the actual specific capacity of battery, and preparation method is simple.
Carbon fiber modifying spongy graphene-sulfur electrode prepared by the present invention has three-dimensional structure, it is possible to be greatly improved the negative of sulphur
Carrying capacity and surface density, the content of sulphur is up to more than 80%, and area ratio capacity reaches 10mAh/cm2, and have good
Cyclical stability and high rate performance, under 1C multiplying power, the area ratio capacity of electrode is up to 5mAh/cm2。
The lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive pole of the present invention is applied in lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the first charge-discharge curve map of button cell under 0.1C charge-discharge magnification, and in figure, a is the carbon of test 1 preparation
The first charge-discharge curve of the battery of fiber reinforcement three-dimensional sponge shape graphene-sulfur electrode；B is the three-dimensional sea of test 2 preparation
The first charge-discharge curve of the battery of continuous shape graphene-sulfur electrode；
Fig. 2 is the cycle performance figure of button cell, and in figure, a is the fibre reinforced three-dimensional sponge shape Graphene of test 1 preparation
The cycle performance figure of the battery of-sulfur electrode；B is the circulation of the battery of the three-dimensional sponge shape graphene-sulfur electrode of test 2 preparation
Performance map；
Fig. 3 is the high rate performance figure of battery, and in figure, a is the fibre reinforced three-dimensional sponge shape graphene-sulfur of test 1 preparation
The high rate performance figure of the battery of electrode；B is the most forthright of the battery of the three-dimensional sponge shape graphene-sulfur electrode of test 2 preparation
Can figure.
Detailed description of the invention
Detailed description of the invention one: a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode of present embodiment is
Elemental sulfur is dispersed among the hole within carbon fiber modifying spongy graphene, wherein the quality hundred of elemental sulfur in positive electrode
Mark is 40%～85%, and the mass percent of carbon fiber is 2%～8%, and the mass percent of Graphene is 7%～58%.
Detailed description of the invention two: present embodiment mass fraction of elemental sulfur unlike detailed description of the invention one is
50%～80%, the mass fraction of carbon fiber is 5%～6%, and the mass percent of Graphene is 14%～45%.Other with tool
Body embodiment one is identical.
Detailed description of the invention three: present embodiment mass fraction of elemental sulfur unlike detailed description of the invention one is 70%,
The mass fraction of carbon fiber is 10%, and the mass percent of Graphene is 20%.Other is identical with detailed description of the invention one.
Detailed description of the invention four: present embodiment elemental sulfur described in unlike one of detailed description of the invention one to three is for rising
China sulphur S8.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: outside the carbon fiber that present embodiment is described unlike one of detailed description of the invention one to four
Footpath is 50～150nm, internal diameter 15～90nm, a length of 50～150 μm；Other and one of detailed description of the invention one to four phase
With.
Detailed description of the invention six: a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur described in detailed description of the invention one is just
The preparation method of pole material, sequentially includes the following steps:
One, weigh carbon fiber, Graphene and elemental sulfur respectively, the quality summation of carbon fiber, Graphene and elemental sulfur is calculated as
M, wherein the quality of elemental sulfur accounts for the 40%～85% of M, and the quality of the quality of carbon fiber accounts for the 2%～8% of M, Graphene
Quality account for the 7%～58% of M；After first Graphene being aoxidized, it is added to the water and stirs, obtain graphene oxide and divide
Dissipate liquid；Again carbon fiber is joined in graphene oxide dispersion, stirring, obtain mixed liquor；Wherein graphene oxide dispersion
The concentration of middle graphene oxide is 3.0～5.0mg/ml；
Two, mixed liquor is transferred in water heating kettle, under conditions of temperature is 180～200 DEG C after hydro-thermal reaction 18～20h,
Obtain carbon fiber modifying three-dimensional sponge shape Graphene hydrogel；Again carbon fiber modifying three-dimensional sponge shape Graphene hydrogel is carried out
Freeze-drying, obtains carbon fiber modifying three-dimensional sponge shape Graphene；
Three, carbon fiber modifying three-dimensional sponge shape Graphene is thinly sliced, and elemental sulfur is sprinkled upon equably sheet surface, put
Enter in vacuum tank, be 10 in vacuum-4～10-2It is heated to 155～160 DEG C under conditions of kPa and keeps 2～5h, obtaining lithium sulphur
Battery fibre reinforced three-dimensional grapheme-sulphur positive electrode.
Detailed description of the invention seven: outside present embodiment carbon fiber described in step one unlike detailed description of the invention six
Footpath is 50～150nm, internal diameter 15～90nm, a length of 50～150 μm.Other is identical with detailed description of the invention six.
Detailed description of the invention eight: in present embodiment step one unlike detailed description of the invention six or seven, graphene oxide divides
Dissipating the concentration of graphene oxide in liquid is 4.0mg/ml；Carbon fiber is 1:10 with the mass ratio of graphene oxide.Other with tool
Body embodiment six or seven is identical.
Detailed description of the invention nine: hydro-thermal reaction in present embodiment step 2 unlike one of detailed description of the invention six to eight
Temperature be 190 DEG C, the reaction time is 19h.Other is identical with one of detailed description of the invention six to eight.
Detailed description of the invention ten: the vacuum in present embodiment step 3 unlike one of detailed description of the invention six to eight
It is 10-2KPa, the temperature of heating is 158 DEG C, and the retention time is 4h.Other is identical with one of detailed description of the invention six to eight.
Detailed description of the invention 11: utilize the lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur described in detailed description of the invention one
Positive electrode prepares the method for positive pole, particularly as follows: be cut into by lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode
After sheet, the pressure with 2～10MPa is suppressed, obtain carbon fiber modifying spongy graphene that thickness is 100～800 microns-
Sulfur electrode positive pole.
Detailed description of the invention 12: the pressure that present embodiment is suppressed unlike detailed description of the invention 11 is 8MPa；
Other is identical with detailed description of the invention 11.
Detailed description of the invention 13: present embodiment thickness of positive pole unlike detailed description of the invention 11 or 12 is
500 microns.Other is identical with detailed description of the invention 11 or 12.
Beneficial effects of the present invention is verified by example below:
Test 1: the preparation method of the lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode of this test, by following
Step is carried out:
One, after first 150mg Graphene being aoxidized, it is added to the water and stirs, obtain graphene oxide dispersion, wherein
In graphene oxide dispersion, the concentration of graphene oxide is 5.0mg/ml；Again 20mg carbon fiber is joined graphene oxide
In dispersion liquid, stirring, obtain mixed liquor；The external diameter of carbon fiber is 80～120nm, internal diameter 30～50nm, a length of 80～130 μm.
Two, mixed liquor is transferred in water heating kettle, under conditions of temperature is 180 DEG C after hydro-thermal reaction 18h, obtain carbon fine
Dimension modified 3 D spongy graphene hydrogel；Again carbon fiber modifying three-dimensional sponge shape Graphene hydrogel is carried out freeze-drying
24h, obtains carbon fiber modifying three-dimensional sponge shape Graphene；
Three, carbon fiber modifying three-dimensional sponge shape Graphene is thinly sliced, take the thin slice that quality is 2.35mg, and by 9.37mg
Elemental sulfur is sprinkled upon sheet surface equably, puts in vacuum tank, is 10 in vacuum-3160 DEG C it are heated under conditions of kPa
And keep 6h, obtain lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode that quality is 11.72mg.
The lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode utilizing this test to prepare prepares the method for positive pole such as
Under: the pressure of the fibre reinforced three-dimensional grapheme of above-mentioned preparation-sulphur positive electrode 8MPa is suppressed 5 minutes, obtains
A diameter of 10mm, thickness are the sulphur battery fibre reinforced three-dimensional grapheme-sulphur positive pole of 0.5mm.
Test 2: as a comparison, preparation is added without the three-dimensional grapheme-sulfur electrode material of carbon fiber, and concrete grammar is as follows:
The graphene oxide dispersion that graphene oxide concentration is 5.0mg/ml is joined in water heating kettle, is 180 DEG C in temperature
After Water Under thermal response 18h, obtain three-dimensional sponge shape Graphene hydrogel；Again three-dimensional sponge shape Graphene hydrogel is entered
Row freeze-drying 24h, obtains three-dimensional sponge shape Graphene；
Three, three-dimensional sponge shape Graphene is thinly sliced, take the thin slice that quality is 2.34mg, and by 9.34mg elemental sulfur
It is sprinkled upon sheet surface equably, puts in vacuum tank, be 10 in vacuum-2It is heated to 160 DEG C under conditions of kPa and keeps
6h, obtains the three-dimensional sponge shape graphene-sulfur positive electrode that quality is 11.68mg.
The pressure of three-dimensional grapheme-sulphur positive electrode 8MPa is suppressed 5 minutes, obtains a diameter of 10mm, thickness is
The three-dimensional sponge shape graphene-sulfur positive pole of 0.5mm.
By lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive pole and the three-dimensional sponge shape of test 2 preparation of test 1 preparation
Graphene-sulfur positive pole is transferred in argon gas glove box, is all assembled into button cell, the electricity in button cell with lithium anode
Solving liquid is to add two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) and LiNO in a solvent3The solution obtained, wherein solvent
It is the 1 of 1:1 for volume ratio, 3-dioxolanes (DOL) and 1, the mixed liquor of 2-dimethoxy-ethane (DME),
The concentration of two (trimethyl fluoride sulfonyl) imine lithium is lmol/L, LiNO3Concentration be 0.1mol/L.
The electrical property of two button cells of test, wherein under 0.1C charge-discharge magnification, the first charge-discharge of two button cells is bent
Line as it is shown in figure 1, in Fig. 1 a be the battery of fibre reinforced three-dimensional sponge shape graphene-sulfur electrode of test 1 preparation
First charge-discharge curve；B is the first charge-discharge curve of the battery of the three-dimensional sponge shape graphene-sulfur electrode of test 2 preparation；
It will be seen from figure 1 that under 0.1C charge-discharge magnification, discharge and recharge blanking voltage is relative to Li/Li+It is 1.5～3V, this examination
Test described charging and discharging capacity and all refer to the area ratio capacity with positive pole areal calculation.
Under 0.1C charge-discharge magnification, the cycle performance figure of two batteries as in figure 2 it is shown, in figure a be test 1 preparation
The cycle performance figure of the battery of fibre reinforced three-dimensional sponge shape graphene-sulfur electrode；B is the three-dimensional sponge of test 2 preparation
The cycle performance figure of the battery of shape graphene-sulfur electrode；From figure 2 it can be seen that under 0.1C charge-discharge magnification, carbon is fine
The height ratio capacity of dimension enhancing three-dimensional sponge shape graphene-sulfur electrode, up to 450mAh/g, remains to keep after 200 circulations
375mAh/g。
Fig. 3 is the high rate performance figure of two batteries, and in figure, a is the fibre reinforced three-dimensional sponge shape Graphene of test 1 preparation
The high rate performance figure of the battery of-sulfur electrode；B is the multiplying power of the battery of the three-dimensional sponge shape graphene-sulfur electrode of test 2 preparation
Performance map, from figure 3, it can be seen that after fibre reinforced, the battery of three-dimensional sponge shape graphene-sulfur electrode the most forthright
Can have a greater degree of improvement.
Claims (5)
1. the preparation method of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode, it is characterised in that the method
Sequentially include the following steps:
One, weigh carbon fiber, Graphene and elemental sulfur respectively, the quality summation of carbon fiber, Graphene and elemental sulfur is calculated as
M, wherein the quality of elemental sulfur accounts for the 40%～85% of M, and the quality of the quality of carbon fiber accounts for the 2%～8% of M, Graphene
Quality account for the 7%～58% of M；After first Graphene being aoxidized, it is added to the water and stirs, obtain graphene oxide dispersion；
Again carbon fiber is joined in graphene oxide dispersion, stirring, obtain mixed liquor；Wherein graphene oxide dispersion aoxidizes
The concentration of Graphene is 3.0～5.0mg/ml；
Two, mixed liquor is transferred in water heating kettle, under conditions of temperature is 180～200 DEG C after hydro-thermal reaction 18～20h,
To carbon fiber modifying three-dimensional sponge shape Graphene hydrogel；Again carbon fiber modifying three-dimensional sponge shape Graphene hydrogel is carried out cold
Lyophilized dry, obtain carbon fiber modifying three-dimensional sponge shape Graphene；
Three, carbon fiber modifying three-dimensional sponge shape Graphene is thinly sliced, and elemental sulfur is sprinkled upon equably sheet surface, put
Enter in vacuum tank, be 10 in vacuum-5～be heated to 155～160 DEG C under conditions of 1kPa and keep 2～5h, obtain lithium-sulfur cell
Fibre reinforced three-dimensional grapheme-sulphur positive electrode.
The preparation side of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode the most according to claim 1
Method, it is characterised in that in step one, in graphene oxide dispersion, the concentration of graphene oxide is 4.0mg/ml；Carbon fiber and oxygen
The mass ratio of functionalized graphene is 1:10.
The preparation side of a kind of lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode the most according to claim 1
Method, it is characterised in that in step 2, the temperature of hydro-thermal reaction is 190 DEG C, the reaction time is 19h.
4. utilize lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode system prepared by method described in claim 1
The method of standby positive pole, it is characterised in that the method is particularly as follows: by lithium-sulfur cell fibre reinforced three-dimensional grapheme-sulphur positive electrode
After being cut into sheet, the pressure with 2～10MPa is suppressed, and obtains the spongy graphite of carbon fiber modifying that thickness is 100～800 microns
Alkene-sulfur electrode positive pole.
The method preparing positive pole the most according to claim 4, it is characterised in that the thickness of positive pole is 500 microns.
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| CN104900884A (en) * | 2015-05-14 | 2015-09-09 | 南京邮电大学 | Compressible lithium-sulfur battery electrode material and preparation method thereof |
| US10714272B2 (en) * | 2016-01-26 | 2020-07-14 | The Regents Of The University Of California | Graphene frameworks for supercapacitors |
| CN106450423B (en) * | 2016-09-30 | 2019-06-25 | 上海空间电源研究所 | A kind of high specific energy integrated flexible electrode and preparation method thereof |
| CN106602013B (en) * | 2016-12-19 | 2020-11-27 | 中国科学院山西煤炭化学研究所 | Preparation method of sulfur-activated carbon/graphene composite material |
| CN107946582B (en) * | 2017-12-01 | 2020-09-08 | 江苏海四达电源股份有限公司 | Lithium-sulfur battery positive electrode material, preparation method thereof, lithium battery positive electrode and lithium battery |
| CN109873120A (en) * | 2017-12-05 | 2019-06-11 | 中国科学院大连化学物理研究所 | Preparation method without metal collector, the graphene-based lithium-sulphur cell positive electrode of self-supporting |
| CN108630926B (en) * | 2018-05-07 | 2021-09-03 | 中国科学院成都有机化学有限公司 | Lithium-sulfur battery positive electrode containing short carbon fiber filaments and preparation method thereof |
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