CN108281659A - Sulphur anode and lithium-sulfur cell - Google Patents
Sulphur anode and lithium-sulfur cell Download PDFInfo
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to lithium-sulfur cell fields.Sulphur anode, the passivation layer that surface forms the sulfide containing lithium is handled by pre-treatment electrolyte, pre-treatment electrolyte includes solvent, lithium salts and additive, and sulphur anode generates the passivation layer of the sulfide containing lithium with lithium salts and solvent reaction, and additive is conductive high polymer monomer or conductive high polymer monomer derivative.The sulphur positive electrode surface forms stable passivation layer, can prevent the generation of side reaction.
Description
Technical field
The present invention relates to lithium-sulfur cell fields.
Background technology
The theoretical specific capacity of lithium-sulfur cell and respectively than energy up to 1675mAh.g-1And 2600wh.kg-1, it is far above
Commercial lithium ion battery now.Also, sulphur has many advantages, such as resourceful, cheap and less toxic nuisanceless.Therefore,
Lithium-sulfur cell causes global concern, promises to be the high energy density cells of a new generation.But lithium-sulfur cell is but deposited
Poor circulation, self-discharge rate is high and high rate performance is poor the shortcomings of, affect its business application.This is because present lithium
Sulphur battery is generally easily dissolved in using ether solvent as electrolyte solvent, sulphur and the more lithium sulfides of battery discharge intermediate product
In ether solvent.It is acted on by concentration gradient and chemical potential, the more lithium sulfides being dissolved in ether solvent can be arrived across diaphragm
Up to cathode, corrosion reaction occurs with lithium metal, causes the loss of cell active materials.This whole process is known as shuttle effect,
Shuttle effect is to cause the main reason for lithium-sulfur cell cycle life is short, coulombic efficiency is low and self-discharge rate is high.And lithium-sulfur cell
It is exactly because solvent ethers used in lithium-sulfur cell is to sulphur and the electric discharge more lithium sulfides of intermediate product there are the reason of shuttle effect
Solubility it is higher.Therefore, a kind of new method is explored, lithium-sulfur cell is avoided to use ethers electrolyte, is to eliminate shuttle effect
With the effective measures for improving battery performance.
But lithium-sulfur cell cannot directly use esters as electrolyte solvent, the intermediate product because lithium-sulfur cell discharges
It can react with free esters solvent in electrolyte, cause the loss of active material and electrolyte.To avoid this reaction
Generation, researcher proposes sulfurized polyacrylonitrile and the positive systems of sulphur-microporous carbon two in succession, due to the two cell bodies
Sulphur thus can be made with that existing for either as singular molecular entities, can avoid reacting between esters solvent and active material in system
Use carbonates as electrolyte solvent（Zhang S S.Frontiers in Energy Research, 2013, 1:
10.）.From experimental result, the battery of the two systems uses carbonic ester for electrolyte solvent, circulating battery stability compared with
Good, self-discharge rate is low.But limited by electrode structure, sulfur content is difficult to be unfavorable for reality more than 50% in the two positive systems
Existing high-energy density.Therefore, enable the lithium-sulfur cell containing elemental sulfur to use esters electrolyte otherwise, be suppression
Shuttle effect processed and the key measure for improving battery performance.
For this problem, applicant proposed use high concentration esters electrolyte as lithium-sulfur cell electrolyte, China
Number of patent application 201710141187.0.In high concentration esters electrolyte, all solvent molecules have been involved in the molten of lithium ion
Agent, without the presence of free solvent in electrolyte.Therefore, in high concentration electrolyte there is no active material and carbonate solution it
Between reaction, battery have preferable cyclical stability and low self-discharge rate.Also, high concentration electrolyte also has relatively good
Safety, can effectively promote the safety of lithium-sulfur cell.But high concentration electrolyte has viscosity height and conductivity low
Problem, and cost is higher, therefore as lithium-sulfur cell electrolyte, there are certain commercialization difficulty using high concentration electrolyte.
Invention content
It is an object of the present invention to provide one kind having good lithium ion conduction performance, prevents electrolyte from being carried out to it
The sulphur anode of dissolving.It is a further object to provide one kind having good cyclical stability and coulombic efficiency, cost
Low lithium-sulfur cell.
In order to achieve the above-mentioned object of the invention, this patent uses following technical solutions：Sulphur anode, sulphur anode pass through preceding place
The passivation layer that electrolyte processing surface forms the sulfide containing lithium is managed, pre-treatment electrolyte includes solvent, lithium salts and additive, and sulphur is just
Pole generates the passivation layer of the sulfide containing lithium with lithium salts and solvent reaction, and additive is conductive high polymer monomer or conducting polymer list
Syntaxy object.
Preferably, using sulphur simple substance as active material；The concentration of lithium salts in a solvent is higher than 3mol/L.
Preferably, additive is one or more combinations in pyrroles, aniline, thiophene；Solvent includes carbonic ester, carboxylic acid
One or more combinations in ester, phosphate and borate.
Preferably, in sulphur positive electrode surface polymerisation occurs for conductive high polymer monomer or conductive high polymer monomer derivative
Generating has conducting polymer flexible, and conducting polymer makes passivation layer have flexibility.
Preferably, passivation layer is to avoid being in direct contact between electrolyte and the active material of sulphur anode, inhibitory activity object
The passivation layer reacted between matter and electrolyte, passivation layer have lithium ion conduction performance.
Lithium-sulfur cell, including above-mentioned sulphur anode.
Preferably, further including electrolyte, lithium anode, diaphragm and other elements.Further, electrolyte is low dense
Esters electrolyte is spent, low concentration esters electrolyte includes solvent and lithium salts, and the concentration of lithium salts is less than 1.5mol/L.
Preferably, sulphur anode is before assembly by electrolyte pre-treatment, pretreatment mode uses following steps：
（1）Pending sulphur anode, pre-treatment electrolyte, lithium anode, diaphragm and other elements are assembled into lithium-sulfur cell；
（2）After assembled lithium-sulfur cell is stood, carries out charged/discharged cycle and be no less than 1cycle；
（3）Lithium-sulfur cell in glove box after dismantling cycle, the sulphur anode of acquisition be by electrolyte treated sulphur just
Pole.
The sulphur anode for using above-mentioned technical proposal, after being handled by pre-treatment electrolyte, part sulphur in charging process
Positive active material can generate the layer of sulfide passivation containing lithium with lithium salts and solvent reaction in pre-treatment electrolyte, sulphur positive electrode surface,
The passivation layer that sulphur positive electrode surface is stablized can prevent the generation of side reaction.The lithium-sulfur cell of above-mentioned technical proposal is used, sulphur is just
The passivation layer of pole can avoid being in direct contact between electrolyte and active material, anti-between inhibitory activity substance and electrolyte
It answers, it is therefore prevented that dissolving of the electrolyte to active material, passivation layer also have good lithium ion conduction performance, do not interfere with electricity
The migration of lithium ion in pole/electrolyte can significantly inhibit dissolving and migration of more lithium sulfides in ethers electrolyte, and then drop
Influence of the low shuttle effect to battery performance.Conductive high polymer monomer or conductive high polymer monomer derivative additive can be simultaneously
Sulphur positive electrode surface occurs polymerisation and generates with conducting polymer flexible, and it is soft that this layer of conducting polymer so that passivation layer has
Property, the intensity of passivation layer is improved, the volume expansion of sulphur anode in charge and discharge process can be buffered, keeps electrode that there is stabilization
Structure, passivation layer can also keep stable in low concentration electrolyte.Using the lithium-sulfur cell of above-mentioned sulphur anode, charge-discharge machine haircut
Changing, be no longer based on sulphur dissolving and a series of more lithium sulfides generation, but lithium ion pass through passivation layer after directly with work
Property substance sulphur react generate lithium sulfide, after processing sulphur anode can use normal concentration esters electrolyte, will not cause
Side reaction between active material and esters solvent molecule.And due to the variation of reaction mechanism, in lithium-sulfur cell reaction process
The substance for not being dissolvable in water electrolyte generates, and will not cause shuttle effect, thus can significantly improve battery cycle life and library
Human relations efficiency reduces the self-discharge rate of battery.The lithium-sulfur cell can be used for the esters and ether solvent electrolyte of normal concentration, tool
There are preferable cyclical stability, higher coulombic efficiency and low self-discharge rate.
Description of the drawings
Fig. 1：Sulfur electrode activation curve in embodiment 1.
Fig. 2：Lithium-sulfur cell first three weeks charging and discharging curve in embodiment 1.
Specific implementation mode
This patent is further detailed below by embodiment and attached drawing explanation.
In following embodiment and comparative example, abbreviation is described as follows：EC is ethylene carbonate, and DEC is diethyl carbonate,
DOL is 1,3-dioxolane, and DME is glycol dimethyl ether, and TMP is trimethyl phosphate.Py pyrrole monomers, An are aniline monomer,
Th is thiophene monomer, and Thi is 3- tolylthiophenes, and LiTFSI is bis trifluoromethyl sulfimide lithium.
Fresh sulphur anode production method：It is 3 by mass ratio:1 sulphur and the mixture of Ketjen black are after mixing closed
155 under stateo12h is heated under C, obtains sulphur carbon mix.Second, by sulphur carbon mix：Acetylene black：Butadiene-styrene rubber+methylol
Sodium cellulosate=8:1:1 is distributed in suitable water, and electrode slurry is obtained after ball milling 6h.Electrode slurry is coated in drying by third
Aluminium foil surface, through infrared lamp toast 30min after be transferred to 60oIt is dried in vacuo 12h in C baking ovens.4th, the electrode of acquisition is cut out
The disk for being cut into a diameter of 14mm is spare.
Embodiment 1
The pre-treatment electrolyte that 4mol/L is configured using LiTFSI and EC/DEC (v/v, 1/1), is added into pre-treatment electrolyte
1% Py.Using above-mentioned pre-treatment electrolyte, sulphur anode and the assembling button cell such as diaphragm, cathode of lithium.0.1C times of button cell
Battery is disassembled in glove box after being recycled under rate 2 weeks, obtained sulphur is just extremely using pre-treatment electrolyte treated sulphur just
Pole.
The electrolyte of 1mol/L is configured using LiTFSI and EC/DEC (v/v, 1/1).Using above-mentioned low concentration electrolyte,
Treated, and sulphur anode and diaphragm, cathode of lithium etc. assemble button cell.The button cell of acquisition follows after standing under 0.1C multiplying powers
Ring.Record the cyclical stability and coulombic efficiency of battery.
Embodiment 2
The pre-treatment electrolyte that 4mol/L is configured using LiTFSI and EC/DEC (v/v, 1/1), is added into pre-treatment electrolyte
1% Py.Using above-mentioned pre-treatment electrolyte, sulphur anode and the assembling button cell such as diaphragm, cathode of lithium.0.1C times of button cell
Battery is disassembled in glove box after being recycled under rate 2 weeks, obtained sulphur is just extremely using pre-treatment electrolyte treated sulphur just
Pole.
The low concentration electrolyte of 1mol/L is configured using LiTFSI and DOL/DME (v/v, 1/1).It is electrolysed using low concentration
Liquid, treated, and sulphur anode and diaphragm, cathode of lithium etc. assemble button cell.After the button cell standing of acquisition under 0.1C multiplying powers
Cycle.Record the cyclical stability and coulombic efficiency of battery.
Embodiment 3
The pre-treatment electrolyte that 4mol/L is configured using LiTFSI and TMP adds 1% An into pre-treatment electrolyte.Using upper
State pre-treatment electrolyte, sulphur anode and the assembling button cell such as diaphragm, cathode of lithium.After 2 weeks being recycled under button cell 0.1C multiplying powers
Battery is disassembled in glove box, obtained sulphur is just extremely using high concentration electrolyte treated sulphur anode.
The electrolyte of 1mol/L is configured using LiTFSI and TMP.Using above-mentioned low concentration electrolyte, treated, and sulphur is positive
With the assembling button cell such as diaphragm, cathode of lithium.The button cell of acquisition recycles after standing under 0.1C multiplying powers.Record battery follows
Ring stability and coulombic efficiency.
Embodiment 4
The pre-treatment electrolyte that 4mol/L is configured using LiTFSI and TMP adds 1% Thi into pre-treatment electrolyte.Using
Above-mentioned pre-treatment electrolyte, sulphur anode and the assembling button cell such as diaphragm, cathode of lithium.It is recycled 2 weeks under button cell 0.1C multiplying powers
Battery is disassembled in glove box afterwards, obtained sulphur is just extremely using high concentration electrolyte treated sulphur anode.
The electrolyte of 1mol/L is configured using LiTFSI and DOL/DME (v/v, 1/1).Using above-mentioned low concentration electrolyte,
Treated, and sulphur anode and diaphragm, cathode of lithium etc. assemble button cell.The button cell of acquisition follows after standing under 0.1C multiplying powers
Ring.Record the cyclical stability and coulombic efficiency of battery.
Embodiment 5
The pre-treatment electrolyte that 4mol/L is configured using LiTFSI and TMP adds 1% Th into pre-treatment electrolyte.Using upper
State pre-treatment electrolyte, sulphur anode and the assembling button cell such as diaphragm, cathode of lithium.After 2 weeks being recycled under button cell 0.1C multiplying powers
Battery is disassembled in glove box, obtained sulphur is just extremely using high concentration electrolyte treated sulphur anode.
The electrolyte of 1mol/L is configured using LiTFSI and EC/EMC (v/v, 1/1).Using above-mentioned low concentration electrolyte, place
Sulphur anode and diaphragm, cathode of lithium after reason etc. assemble button cell.The button cell of acquisition recycles after standing under 0.1C multiplying powers.
Record the cyclical stability and coulombic efficiency of battery.
Comparative example 1
The electrolyte of 1mol/L is configured using LiTFSI and DOL/DME (v/v, 1/1).Using the electrolyte, sulphur anode and diaphragm,
Cathode of lithium etc. assembles button cell.The button cell of acquisition recycles after standing under 0.1C multiplying powers.Record the stable circulation of battery
Property and coulombic efficiency.
Comparative example 2
The electrolyte of 1mol/L is configured using LiTFSI and EC/DEC (v/v, 1/1).Using the electrolyte, sulphur anode and diaphragm,
Cathode of lithium etc. assembles button cell.The button cell of acquisition recycles after standing under 0.1C multiplying powers.Record the stable circulation of battery
Property and coulombic efficiency.
Comparative example 3
The electrolyte of 1mol/L is configured using LiTFSI and TMP.Using the electrolyte, sulphur anode and the assemblings such as diaphragm, cathode of lithium
Button cell.The button cell of acquisition recycles after standing under 0.1C multiplying powers.Record the cyclical stability and coulombic efficiency of battery.
Comparative example 4
The electrolyte of 4mol/L is configured using LiTFSI and EC/DEC (v/v, 1/1).Using above-mentioned electrolyte, sulphur anode and every
Film, cathode of lithium etc. assemble button cell.Battery is disassembled in glove box after being recycled under button cell 0.1C multiplying powers 2 weeks, is obtained
Sulphur just extremely using high concentration electrolyte treated sulphur anode.
The electrolyte of 1mol/L is configured using LiTFSI and DOL/DME (v/v, 1/1).Using above-mentioned low concentration electrolyte,
Treated, and sulphur anode and diaphragm, cathode of lithium etc. assemble button cell.The button cell of acquisition follows after standing under 0.1C multiplying powers
Ring.Record the cyclical stability and coulombic efficiency of battery.
Specific capacity and coulombic efficiency variation in the cyclic process of battery are pooled in table 1, while testing different implementations
The self-discharge rate of battery in example.The self discharge test method of battery is record the 5th week capacity of battery, battery electric discharge 40% in the 6th week
120h is stood when left and right, records the 6th week specific discharge capacity of battery later.Battery self discharge rate=（5th week capacity-the six weeks
Capacity）/ the five week capacity.
Following table is the cyclical stability and coulombic efficiency for the lithium-sulfur cell that different embodiments obtain.
| Specific capacity 1st/ mAh.g-1 | Coulombic efficiency 1st | Specific capacity 50th | Coulombic efficiency 50th | Specific capacity 100th | Coulombic efficiency 100th | Self-discharge rate | |
| Embodiment 1 | 1072.4 | 99.6% | 986.5 | 99.5% | 933.6 | 99.6% | 1.2% |
| Embodiment 2 | 1123.3 | 92.4% | 972.6 | 90.6% | 823.2 | 90.6% | 10.4% |
| Embodiment 3 | 1065.2 | 99.1% | 989.7 | 99.7% | 936.2 | 99.7% | 1.3% |
| Embodiment 4 | 1165.4 | 92.6% | 986.5 | 90.2% | 841.2 | 91.8% | 9.8% |
| Embodiment 5 | 1121.6 | 96.4% | 975.6 | 99.2% | 926.3 | 99.8% | |
| Comparative example 1 | 1201.3 | 80.3% | 652.9 | 68.5% | - | - | 30.4% |
| Comparative example 2 | 235.6 | - | - | - | - | - | - |
| Comparative example 3 | 225.8 | - | - | - | - | - | - |
| Comparative example 4 | 1062.3 | 98.9% | 426.6 | 93.4% | 156.2 | 90.3% | 8.2% |
As seen from the above table, contain elemental sulfur in sulphur anode, directly esters cannot be used as electrolyte solvent, otherwise battery
It cannot recycle, such as comparative example 2 and comparative example 3.After if sulphur anode uses high concentration electrolyte, electrode surface is contributed to be formed
Certain passivation layer, still, treated, and cycle performance of the electrode assembling in the esters electrolyte of normal concentration is poor, illustrates this
Passivation layer is not sufficiently stable, such as comparative example 4.
When sulphur anode is after the processing of pre-treatment electrolyte, can but have preferable cycle in low concentration esters electrolyte
Stability, and coulombic efficiency weekly is all up to 99% or more, shows that shuttle effect is suppressed significantly, such as embodiment 1-5.Such as
Shown in Fig. 1, significant change has occurred in the discharge curve of lithium-sulfur cell in pre-treatment electrolyte, and entire discharge process shows one
Discharge platform, shape is similar with sulfurized polyacrylonitrile and microporous carbon sulphur positive battery discharge curve, therefore also has similar fill
Discharge mechanism.As shown in Fig. 2, using the processed sulphur anode of pre-treatment electrolyte and low concentration esters electrolyte assembling lithium sulphur electricity
Pond, battery charging and discharging curve is still similar with high concentration esters electrolyte, and has good cyclical stability.Therefore, exist
After being handled in pre-treatment electrolyte, sulphur positive electrode surface generates one layer of stable passivation layer, and sulphur anode is prevented to be electrolysed in esters
Side reaction in liquid.Also, due to the life for avoiding the more lithium sulfides for being dissolvable in water electrolyte in battery charging and discharging reaction process
At shuttle effect will not occur for this kind of battery, be obviously improved the cyclical stability and coulombic efficiency of battery.Meanwhile it handling
Sulphur anode afterwards and the lithium-sulfur cell that low concentration ethers electrolyte assembles are also better than fresh electrode, and the sulphur that also indicates that treated is just
The passivation layer that pole surface generates can effectively inhibit dissolving and migration of more lithium sulfides in ethers electrolyte, and then reduce and wear
Influence of the shuttle effect to battery performance.
Claims (10)
1. sulphur is positive, it is characterised in that sulphur anode handles the passivation layer that surface forms the sulfide containing lithium by pre-treatment electrolyte,
Pre-treatment electrolyte includes solvent, lithium salts and additive, and sulphur anode generates the passivation of the sulfide containing lithium with lithium salts and solvent reaction
Layer, additive is conductive high polymer monomer or conductive high polymer monomer derivative.
2. sulphur anode according to claim 1, it is characterised in that using sulphur simple substance as active material；Lithium salts is in a solvent
Concentration be higher than 3mol/L.
3. sulphur anode according to claim 1, it is characterised in that additive is one kind or several in pyrroles, aniline, thiophene
Kind combination；Solvent includes the combination of one or more of carbonic ester, carboxylate, phosphate and borate.
4. sulphur anode according to claim 1, it is characterised in that conductive high polymer monomer or conductive high polymer monomer derive
Object occurs polymerisation in sulphur positive electrode surface and generates with conducting polymer flexible, and it is soft that conducting polymer so that passivation layer has
Property.
5. sulphur anode according to claim 1, it is characterised in that passivation layer is the active matter for avoiding electrolyte and sulphur anode
It is in direct contact between matter, the passivation layer reacted between inhibitory activity substance and electrolyte, passivation layer has lithium ion conduction performance.
6. lithium-sulfur cell, it is characterised in that including sulphur described in claim 1 anode.
7. lithium-sulfur cell according to claim 6, it is characterised in that further include electrolyte, lithium anode, diaphragm and its
Its element.
8. lithium-sulfur cell according to claim 7, it is characterised in that electrolyte is low concentration electrolyte.
9. lithium-sulfur cell according to claim 8, it is characterised in that low concentration electrolyte includes solvent and lithium salts, and lithium salts
Concentration be less than 1.5mol/L.
10. lithium-sulfur cell according to claim 6, it is characterised in that sulphur anode passes through pre-treatment electrolyte before assembly
Pre-treatment, pretreatment mode use following steps：
（1）Pending sulphur anode, pre-treatment electrolyte, lithium anode, diaphragm and other elements are assembled into lithium-sulfur cell；
（2）After assembled lithium-sulfur cell is stood, carries out charged/discharged cycle and be no less than 1cycle；
（3）The sulphur anode of lithium-sulfur cell in glove box after dismantling cycle, acquisition is after the processing of pre-treatment electrolyte
Sulphur anode.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244472A (en) * | 2018-09-26 | 2019-01-18 | 烟台大学 | A kind of lithium-sulfur cell comprising the protectant electrolyte of anode and comprising the electrolyte |
| CN110707364A (en) * | 2019-09-10 | 2020-01-17 | 深圳先进技术研究院 | Method for manufacturing secondary battery |
| CN112313827A (en) * | 2018-11-23 | 2021-02-02 | 株式会社Lg化学 | Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080233467A1 (en) * | 2007-03-19 | 2008-09-25 | Issaev Nikolai N | Lithium cell |
| CN101465441A (en) * | 2009-01-06 | 2009-06-24 | 清华大学 | Lithium sulphur battery using graphite as cathode and preparation method thereof |
| CN102983361A (en) * | 2012-11-23 | 2013-03-20 | 中国人民解放军国防科学技术大学 | Electrolyte for Li-S battery, preparation method thereof, and Li-S battery containing same |
| CN104466183A (en) * | 2014-12-03 | 2015-03-25 | 湘潭大学 | Positive electrode material of polypyrrole lithium sulfur battery and preparation method of positive electrode material |
| CN105322132A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院上海硅酸盐研究所 | Positive electrode of lithium-sulfur battery with multifunctional elastic protection layer |
| WO2016068641A1 (en) * | 2014-10-31 | 2016-05-06 | 주식회사 엘지화학 | Lithium sulfur battery and method for producing same |
| CN105702914A (en) * | 2016-04-19 | 2016-06-22 | 山东大学 | Method for protecting anode of lithium sulphur battery |
| CN105789557A (en) * | 2016-05-26 | 2016-07-20 | 厦门大学 | Lithium-sulfur pole piece with function protection layer and preparation method and application thereof |
| CN106415911A (en) * | 2014-05-29 | 2017-02-15 | 得克萨斯州大学系统董事会 | Electrolyte additives for lithium-sulfur batteries |
| CN106784728A (en) * | 2017-01-19 | 2017-05-31 | 上海德朗能动力电池有限公司 | Conduction high polymer cladding sulfur electrode material and its manufacture method of a kind of high-capacity secure |
| CN106784855A (en) * | 2016-12-02 | 2017-05-31 | 西安瑟福能源科技有限公司 | A kind of unmanned plane manufacture method of high temperature modification lithium ion battery |
| CN107221660A (en) * | 2017-06-15 | 2017-09-29 | 北京理工大学 | A kind of flexible lithium sulfur battery anode material |
| WO2017171505A1 (en) * | 2016-03-31 | 2017-10-05 | 서울대학교산학협력단 | Electrode surface-coated by polymer film, method for producing same, and secondary battery comprising same |
-
2018
- 2018-01-18 CN CN201810048441.7A patent/CN108281659A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080233467A1 (en) * | 2007-03-19 | 2008-09-25 | Issaev Nikolai N | Lithium cell |
| CN101465441A (en) * | 2009-01-06 | 2009-06-24 | 清华大学 | Lithium sulphur battery using graphite as cathode and preparation method thereof |
| CN102983361A (en) * | 2012-11-23 | 2013-03-20 | 中国人民解放军国防科学技术大学 | Electrolyte for Li-S battery, preparation method thereof, and Li-S battery containing same |
| CN106415911A (en) * | 2014-05-29 | 2017-02-15 | 得克萨斯州大学系统董事会 | Electrolyte additives for lithium-sulfur batteries |
| CN105322132A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院上海硅酸盐研究所 | Positive electrode of lithium-sulfur battery with multifunctional elastic protection layer |
| WO2016068641A1 (en) * | 2014-10-31 | 2016-05-06 | 주식회사 엘지화학 | Lithium sulfur battery and method for producing same |
| CN104466183A (en) * | 2014-12-03 | 2015-03-25 | 湘潭大学 | Positive electrode material of polypyrrole lithium sulfur battery and preparation method of positive electrode material |
| WO2017171505A1 (en) * | 2016-03-31 | 2017-10-05 | 서울대학교산학협력단 | Electrode surface-coated by polymer film, method for producing same, and secondary battery comprising same |
| CN105702914A (en) * | 2016-04-19 | 2016-06-22 | 山东大学 | Method for protecting anode of lithium sulphur battery |
| CN105789557A (en) * | 2016-05-26 | 2016-07-20 | 厦门大学 | Lithium-sulfur pole piece with function protection layer and preparation method and application thereof |
| CN106784855A (en) * | 2016-12-02 | 2017-05-31 | 西安瑟福能源科技有限公司 | A kind of unmanned plane manufacture method of high temperature modification lithium ion battery |
| CN106784728A (en) * | 2017-01-19 | 2017-05-31 | 上海德朗能动力电池有限公司 | Conduction high polymer cladding sulfur electrode material and its manufacture method of a kind of high-capacity secure |
| CN107221660A (en) * | 2017-06-15 | 2017-09-29 | 北京理工大学 | A kind of flexible lithium sulfur battery anode material |
Non-Patent Citations (3)
| Title |
|---|
| SONG JONGCHAN ET AL: ""In situ coating of Poly(3,4-ethylenedioxythiophene) on sulfur cathode for high performance lithium-sulfur batteries"", 《JOURNAL OF POWER SOURCES》 * |
| 刘帅等: ""高性能锂硫电池研究进展"", 《物理化学学报》 * |
| 李艳容: "《导电聚合物应用于锂硫电池并改善其电化学性能》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109244472A (en) * | 2018-09-26 | 2019-01-18 | 烟台大学 | A kind of lithium-sulfur cell comprising the protectant electrolyte of anode and comprising the electrolyte |
| CN112313827A (en) * | 2018-11-23 | 2021-02-02 | 株式会社Lg化学 | Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same |
| US11631896B2 (en) | 2018-11-23 | 2023-04-18 | Lg Energy Solution, Ltd. | Electrolyte for lithium-sulfur battery and lithium-sulfur battery comprising same |
| CN110707364A (en) * | 2019-09-10 | 2020-01-17 | 深圳先进技术研究院 | Method for manufacturing secondary battery |
| CN110707364B (en) * | 2019-09-10 | 2021-01-01 | 深圳先进技术研究院 | Method for manufacturing secondary battery |
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