CN103887474B - Method for improving capacity and cyclic stability of lithium-sulfur battery cathode material - Google Patents
Method for improving capacity and cyclic stability of lithium-sulfur battery cathode material Download PDFInfo
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- CN103887474B CN103887474B CN201410136586.4A CN201410136586A CN103887474B CN 103887474 B CN103887474 B CN 103887474B CN 201410136586 A CN201410136586 A CN 201410136586A CN 103887474 B CN103887474 B CN 103887474B
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- 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 invention discloses a method for improving the capacity and cyclic stability of a lithium-sulfur battery cathode material, and is characterized by providing a novel composite adhesive formula and a preparation process of a cathode material and aiming to prepare a lithium-sulfur battery cathode material with high specific capacity and high energy density. The method comprises the steps of mixing activated porous conductive carbon and other conductive agents with sulfur according to a certain ratio, adding a certain quantity of multi-component high-molecular polymer as an adhesive and acetonitrile as a solvent, mixing multi-component high-molecular polymer and acetonitrile with a stainless steel ball with a certain diameter, and treating the mixture for several hours by using a ball milling method to obtain paste of the lithium-sulfur battery cathode material. The adhesive not only can be used for bonding an active material, but also can play a role in coating sulfur and sulfides; the adhesive is added in an early preparation stage to ensure that a uniformly-distributed and thickness-controllable thin polymer layer is formed on the surface of each of sulfur and conductive agent through the ball milling method, so that the direct contact among electrolyte, sulfur and a compound thereof is effectively avoided, the dissolution of sulfur and the decomposition of electrolyte are reduced, and the cyclic stability of a lithium-sulfur battery is improved.
Description
Technical field
The invention belongs to high-energy secondary battery preparing technical field is and in particular to a kind of high energy lithium sulfur battery anode material
Preparation technology, novel binders and its coating process.
Background technology
Lithium rechargeable battery is a kind of best electrochmical power source of current combination property, is widely used in mobile phone, notebook
In the portable type electronic products such as video camera.But the appearance with various novel electric vehicles and popularization are it is desirable to lithium ion battery
There is higher power density and energy density.Existing lithium ion battery technology cannot meet the above-mentioned marketization and require,
Therefore exploitation and design novel secondary cell reaction system and associated materials just become high-energy secondary battery technology future development
Crucial.Recently, as emerging secondary cell system, lithium-sulfur cell causes the extensive concern of people.Because it has super height
Theoretical energy density, up to 2600Wh Kg-1, being expected to replacement lithium ion battery becomes the last secondary electricity of combination property of future generation
Pond.Further, since the positive electrode sulfur rich reserves of lithium-sulfur cell, cheap so that its have more commercialization on a large scale should
Use prospect.
But, because sulfur has natural insulation, huge change in volume in addition, and then cause very serious capacity to decline
Subtract, which limits the commercial applications of lithium-sulfur cell.Research finds to lead to the main cause of lithium-sulfur cell capacity deep fades
The sulfur being because in material is partially dissolved in electrolyte and leads to the power that the loss of electroactive substance and sulfur are reacted with lithium
Factor is restricted.
Research finds, carrying out surface coating decoration modification to lithium-sulfur cell electrochemical active material can be to a certain extent
Stoping the directly contact of electrolyte and sulfur, reducing sulfur and the dissolving of sulfide and the decomposition of electrolyte, thus improving lithium-sulfur cell
Comprehensive electrochemical.At present, modified mainly such as poly- using conducting polymer to the coating decoration of lithium sulfur battery anode material
Aniline etc. is coated, and solves the problems, such as that its electron conduction is poor.But these coating decoration modifications not only need the preparation of complexity
Technique, considerably increases material preparation cost, and final effect is not notable.
Binding agent has to use for a kind of material in preparing as a kind of battery plus-negative plate electrode, is in order to by both positive and negative polarity material
In material, various compositions are bonded together formation paste, carry out both positive and negative polarity electrode slice coating and then prepare electrode.At present, test
Common one-component macromolecule polymer material is generally adopted by room and commercial production, such as Kynoar（PVDF）With
Politef（PTFE）Deng, and the research report seldom about the type component of binding agent, battery performance being affected.This
Bright disclose a kind of formula of novel high polymer binding agent, the excellent properties of comprehensive dissimilar macromolecular material, simultaneously in profit
When preparing anode sizing agent with high polymer binder, the joining day of binding agent is shifted to an earlier date, and bonding is regulated and controled using ball-milling technology
Agent, in the apparent condition of sulfur and its compound, regulates and controls interfacial structure, reaches the effect not only playing binding agent but also plays clad
Effect, simplifies preparation technology, reduces synthesis cost, and can significantly improve lithium-sulfur cell combination property.
Content of the invention
The technical problem to be solved is：A kind of new binder formula and positive electrode preparation work are provided
Skill, preparation has the lithium-sulfur cell of height ratio capacity and high-energy-density.Novel binders also have except the cementation of itself
Cladding sulfur and the effect of sulfide, add binding agent by ball-milling technology in early stage preparatory phase, can be on sulfur and conductive agent surface
The polymer electrolyte thin layer that one layer of formation is evenly distributed, thickness is controlled, this thin layer can stop sulfur and sulfide and electrolyte contacts, subtract
The loss of few sulfur, alleviates active substance volumetric expansion, and then improves the cyclical stability of lithium-sulfur cell.
The technical scheme is that：A kind of raising lithium sulfur battery anode material specific capacity and the method for cyclical stability,
Conductive agent is mixed according to certain mol proportion with sulfur, is simultaneously introduced a certain amount of multicomponent high molecular polymer as binding agent,
Using water or acetonitrile as solvent, after mixing according to suitable ratio of grinding media to material with the stainless steel ball of certain diameter, entered using ball grinding method
After some hours of row ball-milling treatment, just obtain the slurry of lithium sulfur battery anode material, be then applied on aluminium foil, punching press after being dried
After becoming a certain size disk, just obtain lithium-sulphur cell positive electrode.
The above conductive agent is：Acetylene black, Super P, Graphene, CNT, in activation porous, electrically conductive carbon
Kind, the mol ratio of carbon and sulfur is 70：30 to 10：Between 90 scopes；
The above high molecular polymer is：Polyvinylpyrrolidone（PVP）, polyethylene glycol oxide（PEO）, Kynoar
（PVDF）, carboxymethyl cellulose（CMC）With polystyrenebutadienes copolymer（SBR）In two kinds, mol ratio used is 9：1 to
1：Between 9 scopes；
The above ball-milling treatment time between 10 minutes to 20 hours, rotating speed at 2000 revs/min to 20000 revs/min,
A small amount of water is added as cosolvent in mechanical milling process；
In 3～200nm, shared mass ratio is 0.5～10% to the thickness of the above polymeric PTC materials layer.
The present invention is a kind of method improving lithium sulfur battery anode material capacity and cyclical stability, has the characteristics that：
First, to prepare the framing structure of sulfur and conductive carbon using simple ball grinding method, it is to avoid complicated preparation technology,
Reduce synthesis cost, be conducive to large-scale production.
Second, adopting NEW TYPE OF COMPOSITE binding agent, two kinds of high molecular polymers using proper proportion are used as binding agent, increase
The strong stability of electrode structure.
Third, the addition of binding agent advances to the preparatory phase of positive electrode, make binding agent both play to bond active substance
Serve as the double effects of positive electrode clad again.
Positive electrode through special process preparation obtained as above, its specific capacity improves a lot, and particularly it follows
Ring stability is greatly improved, and the lithium sulfur battery anode material using the preparation of this method is described, had both comprised nanoscale scattered
Active substance sulfur, has played binding agent as the effect of clad simultaneously again, can effectively stop electrolyte and sulfur and its change
The directly contact of compound, reduces the dissolving of sulfur and the decomposition of electrolyte, solves the cyclical stability of lithium-sulfur cell generally existing
The problem of difference.Low cost of the present invention, process route is simple, and energy consumption is low, is suitable for industrial volume production.
Brief description
Fig. 1 is the charging and discharging curve figure that the lithium sulfur battery anode material prepared by case study on implementation 1 is described.
Fig. 2 is the cycle performance figure that the lithium sulfur battery anode material prepared by case study on implementation 1 is described.
Specific embodiment
For a better understanding of the present invention, with reference to example, the present invention will be further described, but application claims are protected
Shield scope is not limited to the express ranges of example.
Case study on implementation 1
By sulfur and activation porous, electrically conductive carbon（The mol ratio of wherein sulfur and activation porous, electrically conductive carbon is 1:1）Weigh in proportion,
It is 10 by the mol ratio with sulfur：1 ratio adds a certain amount of binding agent（PVP：PEO=1：1）, insert in ball grinder, by ball material
Than for 2：1 a certain amount of abrading-ball of addition, adds a small amount of moisture content to be conducive to the dissolving of binding agent, carries out ball milling in ball mill, if
The rotating speed of Place grinding machine becomes 20000 revs/min, and ball milling, after 2 hours, takes out abrasive material.The positive pole material of lithium sulfur electrode is obtained after separating
Material.
The preparation of positive plate and button cell test.Active matter with the mixture of ball milling as electrode, is tuned into slurry with water.
Slurry is coated in current collector aluminum foil, is vacuum dried 8～10 hours at 60 DEG C, remove solvent and moisture, and in 8～
It is compacted under the pressure of 12MPa, make to contact closely between the powder of electrode.Strike out the positive pole disk of a diameter of 14mm size again, it
Prepare assembling after 8-10 hour is dried afterwards again in vacuum drying oven.Battery enters luggage in the dry glove box full of argon
Join.Test battery adopts CR2025 button cell, and negative pole adopts metal lithium sheet, and barrier film adopts Celgard2400 film, and electrolyte is
1M LiTFSI, 0.25M LiNO3It is dissolved in 1:1DME:In DOL.Battery testing is in blue electricity battery test system（LAND CT-
2001A）Carry out, charging/discharging voltage scope is 1.6-2.6V, 25 DEG C of test temperature.
Fig. 1 is prepared lithium sulfur battery anode material in 100mA g-1Electric current density under charging and discharging curve, it is first
Secondary charging and discharging capacity is respectively 977.3 and 934.9mAh g-1.Fig. 2 is prepared lithium sulfur battery anode material in 100mA
g-1Cycle performance and coulombic efficiency figure, first coulombic efficiency be up to 95.6%, its discharge and recharge specific volume after continuous circulation 20 times
Amount remains at 828.1 and 823.1mAh g-1, show excellent cyclical stability.
Case study on implementation 2
By sulfur and activation porous, electrically conductive carbon（The mol ratio of wherein sulfur and activation porous, electrically conductive carbon is 9:1）Weigh in proportion,
In molar ratio be sulfur, carbon, binding agent be 9：1：1 ratio adds a certain amount of binding agent（PVP：PEO=1：4）, insert ball grinder
Interior, it is 2 by ratio of grinding media to material：1 a certain amount of abrading-ball of addition, adds a small amount of moisture content to be conducive to the dissolving of binding agent, enters in ball mill
Row ball milling, the rotating speed of setting ball mill becomes 20000 revs/min, and ball milling, after 4 hours, takes out abrasive material.Lithium sulfur electrode is obtained after separating
Positive electrode.Method according to case study on implementation 1 is assembled into after battery, in 100mA g-1Electric current density under carry out performance survey
Examination, first discharge specific capacity is 923.9mAh g-1, after circulating 20 times, specific discharge capacity is maintained at 817.7mAh g-1.
Case study on implementation 3
By sulfur and acetylene black and binding agent（The mol ratio of wherein sulfur and acetylene black and binding agent is 6：4：1）Claim in proportion
Measure, binding agent is（PVP：PEO=1：9）, insert in ball grinder, be 3 by ratio of grinding media to material：1 a certain amount of abrading-ball of addition, adds a small amount of
Moisture content is conducive to the dissolving of binding agent, carries out ball milling in ball mill, and the rotating speed of setting ball mill becomes 20000 revs/min, ball milling
After 10 hours, take out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.Method according to case study on implementation 1 is assembled into battery
Afterwards, in 100mA g-1Electric current density under carry out performance test, first discharge specific capacity be 1239.1mAh g-1, circulate 20 times
Specific discharge capacity is maintained at 957.7mAh g afterwards-1.
Case study on implementation 4
By sulfur and acetylene black（The mol ratio of wherein sulfur and acetylene black is 9:1）Weigh in proportion, in molar ratio for sulfur, carbon,
Binding agent is 5：4：1 ratio adds a certain amount of binding agent（PVP：PEO=9：1）, insert in ball grinder, be 3 by ratio of grinding media to material：1
Add a certain amount of abrading-ball, add a small amount of moisture content to be conducive to the dissolving of binding agent, ball mill carries out ball milling, ball mill is set
Rotating speed become 20000 revs/min, ball milling is after 10 hours, takes out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.According to
After the method for case study on implementation 1 is assembled into battery, in 100mA g-1Electric current density under carry out performance test, first discharge specific capacity
For 1493.9mAh g-1, after circulating 20 times, specific discharge capacity is maintained at 1157.7mAh g-1.
Case study on implementation 5
By sulfur and Super P（The mol ratio of wherein sulfur and Super P is 9:1）Weigh in proportion, in molar ratio for sulfur,
Carbon, binding agent are 5：4：1 ratio adds a certain amount of binding agent（PVP：PVDF=9：1）, insert in ball grinder, by ratio of grinding media to material
For 3：1 a certain amount of abrading-ball of addition, adds a small amount of moisture content to be conducive to the dissolving of binding agent, carries out ball milling in ball mill, setting
The rotating speed of ball mill becomes 20000 revs/min, and ball milling, after 10 hours, takes out abrasive material.The positive pole material of lithium sulfur electrode is obtained after separating
Material.Method according to case study on implementation 1 is assembled into after battery, in 100mA g-1Electric current density under carry out performance test, put first
Electric specific capacity is 1591.9mAhg-1, after circulating 20 times, specific discharge capacity is maintained at 1253.7mAh g-1.
Case study on implementation 6
By sulfur and Super P and binding agent（The mol ratio of wherein sulfur and Super P and binding agent is 6：4：1）Claim in proportion
Measure, binding agent is（PVP：PVDF=1：9）, insert in ball grinder, be 3 by ratio of grinding media to material：1 a certain amount of abrading-ball of addition, adds a small amount of
Moisture content is conducive to the dissolving of binding agent, carries out ball milling in ball mill, and the rotating speed of setting ball mill becomes 20000 revs/min, ball milling
After 10 hours, take out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.Method according to case study on implementation 1 is assembled into battery
Afterwards, in 100mA g-1Electric current density under carry out performance test, first discharge specific capacity be 1181.9mAh g-1, circulate 20 times
Specific discharge capacity is maintained at 983.7mAh g afterwards-1.
Case study on implementation 7
By sulfur and Super P and binding agent（The mol ratio of wherein sulfur and Super P and binding agent is 6：4：1）Claim in proportion
Measure, binding agent is（PVDF：PEO=1：9）, insert in ball grinder, be 3 by ratio of grinding media to material：1 a certain amount of abrading-ball of addition, adds a small amount of
Moisture content is conducive to the dissolving of binding agent, carries out ball milling in ball mill, and the rotating speed of setting ball mill becomes 20000 revs/min, ball milling
After 5 hours, take out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.Method according to case study on implementation 1 is assembled into battery
Afterwards, in 100mA g-1Electric current density under carry out performance test, first discharge specific capacity be 1271.3mAh g-1, circulate 20 times
Specific discharge capacity is maintained at 993.7mAh g afterwards-1.
Case study on implementation 8
By sulfur and activation porous, electrically conductive carbon and binding agent（Wherein sulfur and the mol ratio of activation porous, electrically conductive carbon and binding agent are
6：4：1）Weigh in proportion, binding agent is（PVdF：PEO=9：1）, insert in ball grinder, be 3 by ratio of grinding media to material：1 addition is a certain amount of
Abrading-ball, add a small amount of moisture content to be conducive to the dissolving of binding agent, ball mill carry out ball milling, the rotating speed of setting ball mill becomes
20000 revs/min, ball milling, after 1 hour, takes out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.According to case study on implementation 1
After method is assembled into battery, in 100mAg-1Electric current density under carry out performance test, first discharge specific capacity be 1071.3mAh
g-1, after circulating 20 times, specific discharge capacity is maintained at 963.2mAh g-1.
Case study on implementation 9
By sulfur and activation porous, electrically conductive carbon and binding agent（Wherein sulfur and the mol ratio of activation porous, electrically conductive carbon and binding agent are
6：4：1）Weigh in proportion, binding agent is（PVDF：PVP=9：1）, insert in ball grinder, be 3 by ratio of grinding media to material：1 addition is a certain amount of
Abrading-ball, add a small amount of moisture content to be conducive to the dissolving of binding agent, ball mill carry out ball milling, the rotating speed of setting ball mill becomes
20000 revs/min, ball milling, after 30 minutes, takes out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.According to case study on implementation 1
After method is assembled into battery, in 100mAg-1Electric current density under carry out performance test, first discharge specific capacity be 861.3mAh
g-1, after circulating 20 times, specific discharge capacity is maintained at 753.2mAh g-1.
Case study on implementation 10
By sulfur and activation porous, electrically conductive carbon and binding agent（Wherein sulfur and the mol ratio of activation porous, electrically conductive carbon and binding agent are
8：3：1）Weigh in proportion, binding agent is（PVDF：PVP=1：9）, insert in ball grinder, be 3 by ratio of grinding media to material：1 addition is a certain amount of
Abrading-ball, add a small amount of moisture content to be conducive to the dissolving of binding agent, ball mill carry out ball milling, the rotating speed of setting ball mill becomes
20000 revs/min, ball milling, after 10 hours, takes out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.According to case study on implementation 1
After method is assembled into battery, in 100mAg-1Electric current density under carry out performance test, first discharge specific capacity be 1581.3mAh
g-1, after circulating 20 times, specific discharge capacity is maintained at 1263.5mAh g-1.
Case study on implementation 11
By sulfur and activation porous, electrically conductive carbon and binding agent（Wherein sulfur and the mol ratio of activation porous, electrically conductive carbon and binding agent are
8：3：1）Weigh in proportion, binding agent is（CMC：SBR=1：1）, insert in ball grinder, be 3 by ratio of grinding media to material：1 addition is a certain amount of
Abrading-ball, adds a small amount of moisture content to be conducive to the dissolving of binding agent, carries out ball milling in ball mill, and the rotating speed of setting ball mill becomes
20000 revs/min, ball milling, after 10 hours, takes out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.According to case study on implementation 1
After method is assembled into battery, in 100mAg-1Electric current density under carry out performance test, first discharge specific capacity be 1381.3mAh
g-1, after circulating 20 times, specific discharge capacity is maintained at 1053.4mAh g-1.
Case study on implementation 12
By sulfur and activation porous, electrically conductive carbon and binding agent（Wherein sulfur and the mol ratio of activation porous, electrically conductive carbon and binding agent are
4：5：1）Weigh in proportion, binding agent is（CMC：SBR=3：2）, insert in ball grinder, be 4 by ratio of grinding media to material：1 addition is a certain amount of
Abrading-ball, adds a small amount of moisture content to be conducive to the dissolving of binding agent, carries out ball milling in ball mill, and the rotating speed of setting ball mill becomes
20000 revs/min, ball milling, after 5 hours, takes out abrasive material.The positive electrode of lithium sulfur electrode is obtained after separating.According to case study on implementation 1
After method is assembled into battery, in 100mAg-1Electric current density under carry out performance test, first discharge specific capacity be 1289.3mAh
g-1, after circulating 20 times, specific discharge capacity is maintained at 1013.7mAh g-1.
Claims (2)
1. a kind of method improving lithium sulfur battery anode material capacity and cyclical stability, is characterized in that：Conductive agent is pressed with sulfur
According to certain mol proportion mixing, it is simultaneously introduced a certain amount of high molecular polymer Polyvinylpyrrolidone (PVP), polyethylene glycol oxide
(PEO) and carboxymethyl cellulose (CMC), in polystyrenebutadienes copolymer (SBR) any two kinds as Bicomponent binder,
The mol ratio of two kinds of binding agents is 9：1 to 1：Between 9 scopes, using water or acetonitrile as solvent, the stainless steel ball with certain diameter
After the mixing of suitable ratio of grinding media to material, the slurry that ball milling just obtains lithium sulfur battery anode material, ball milling are carried out using ball grinding method
Process time between 10 hours to 20 hours, 20000 revs/min of rotating speed, be then applied on aluminium foil, strike out certain after being dried
After the disk of size, just obtain lithium-sulphur cell positive electrode.
2. a kind of method improving lithium sulfur battery anode material capacity and cyclical stability as claimed in claim 1, described leads
Electric agent is：Acetylene black, Super P, Graphene, CNT, activation one of porous, electrically conductive carbon, conductive agent and sulfur mole
Than 70：30 to 10：Between 90 scopes.
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| CN104505516B (en) * | 2014-12-29 | 2017-02-22 | 北京化工大学 | Positive active material for lithium sulfur battery and preparation method of positive active material |
| CN104779368B (en) * | 2015-04-15 | 2019-04-16 | 东莞市创明电池技术有限公司 | A kind of preparation method of based lithium-ion battery positive plate and obtained lithium ion battery |
| CN104900902A (en) * | 2015-06-29 | 2015-09-09 | 北京化工大学 | High-performance lithium sulfur battery |
| CN106711427B (en) * | 2017-02-22 | 2019-07-02 | 清华大学深圳研究生院 | A kind of positive material for lithium-sulfur battery and its application method |
| CN107572486B (en) * | 2017-09-04 | 2020-05-19 | 北京化工大学 | Nano sulfur particles, preparation and preparation of lithium-sulfur battery positive electrode |
| CN107863509A (en) * | 2017-10-23 | 2018-03-30 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of polymer overmold sulphur carbon composite anode material |
| CN108987706A (en) * | 2018-07-18 | 2018-12-11 | 东莞理工学院 | A kind of lithium-sulfur cell long-life composite sulfur active material and preparation method thereof |
| CN112635707A (en) * | 2019-09-24 | 2021-04-09 | 中航锂电技术研究院有限公司 | Composite positive electrode of lithium-sulfur battery, preparation method of composite positive electrode and lithium-sulfur battery |
| CN112881194A (en) * | 2021-01-21 | 2021-06-01 | 北京理工大学 | Lithium battery in-situ force thermal coupling loading device for X-ray CT system |
| CN114792804B (en) * | 2022-04-28 | 2023-07-25 | 北京理工大学重庆创新中心 | 3D printing positive electrode ink, positive electrode forming method using same and application |
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| JP2002110237A (en) * | 2000-08-17 | 2002-04-12 | Samsung Sdi Co Ltd | Positive electrode active material composition for lithium-sulfur battery, its manufacturing method and lithium-sulfur battery |
| CN101399329B (en) * | 2007-09-26 | 2011-02-09 | 北京化工大学 | Manufacturing method of positive pole plate of lithium-sulfur cell |
| CN103579583B (en) * | 2012-07-25 | 2015-08-12 | 中国科学院大连化学物理研究所 | A kind of manufacture method of lithium-sulphur cell positive electrode |
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