CN107293694A - Polysulphide polymer composite its preparation method and application - Google Patents
Polysulphide polymer composite its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of polysulphide polymer composite and preparation method and application.The step of preparation method of polysulphide polymer composite of the present invention includes preparing the step of containing containing many mercapto monomers, elemental sulfur and porous carbon mix the step of containing many mercapto monomers solution, formation and carrying out heating polymerisation to mixture.Polysulphide polymer composite material and preparation method thereof of the present invention utilizes the electric conductivity and pattern diversity of porous carbon, polysulphide polymer is combined with porous carbon in situ, so that the polysulphide polymer composite prepared had both remained the pattern of porous carbon, it also can effectively suppress the dissolving of many lithium sulfides and improve the cyclical stability of lithium-sulfur cell.So that positive pole and lithium ion battery containing polysulphide polymer composite have high capacity and excellent cyclical stability.
Description
Technical field
The invention belongs to technical field of lithium ion, relating particularly to a kind of polysulphide polymer composite, it is prepared
Method and application.
Background technology
Lithium ion battery is widely used in intelligent hand with excellent properties such as its high-energy-density, long-life and high voltages
In machine, notebook computer and electric automobile.With smart mobile phone and the lightening of notebook computer, multifunction, giant-screen
And Development of Electric Vehicles, to the energy density requirement more and more higher of battery.But the conventional lithium ion electricity based on intercalation compound
The development of nearly 30 years is passed through in pond, and its energy density has reached its limit, and the rising space is very limited.Therefore, various high energy
The novel battery system of metric density is applied and given birth to, the study hotspot as countries in the world, wherein, lithium-sulfur cell is with up to
It is 2600Wh/kg energy density, relatively low cost of material, easier materials synthesis technique and battery packaging technology, more satisfactory
Charge-discharge performance and one of as most promising technology.
Lithium-sulfur cell is using elemental sulfur or S-containing composite as positive pole, using lithium metal or lithium alloy as the cell body of negative pole
System.Wherein elemental sulfur changes into the corresponding embedding lithium capacity up to 1675mAh/g of lithium sulfide, corresponding voltage platform average out to
2.2V, the corresponding lithium ion capacity of lithium metal is up to 3840mAh/g.The high power capacity of positive and negative electrode and 2.2V average voltage cause
The theoretical energy density of lithium-sulfur cell is up to 2600Wh/kg, and the energy density that can actually reach is also than existing lithium ion battery
It is high 2~3 times, with big advantage.Moreover, compared to traditional lithium such as cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate and LiFePO4 from
The positive electrode of sub- battery, elemental sulfur wide material sources, cheap and nontoxic, this shows that lithium-sulfur cell has relatively low original indirectly
Expect cost and Environmental costs.However, the series of technical of lithium-sulfur cell inherently hinders its practicalization, wherein most
Main the problem of, is attributed at following 2 points：First, sulphur and its high-insulation of discharging product；2nd, the dissolving of many lithium sulfides and its
Shuttle effect (referring to transmission of many sulphions between positive and negative electrode) etc..
In order to improve the electric conductivity of sulphur and suppress the dissolving of many lithium sulfides, most common method is to use conductive porous material
Expect sulfur loaded.In various carriers, porous carbon is one of the most frequently used carrier.Porous carbon have high-specific surface area, high conductivity,
Pattern diversity and the characteristic such as easily prepared.But, because porous carbon is non-polar solid, and many sulphions are polarity, both
Active force be pure physical absorption, absorption affinity is weaker, it is difficult to effectively fix many lithium sulfides.Except porous carbon it
Outside, transistion metal compound has very strong suction-operated to many sulphions, but common transistion metal compound is all insulation
Body or semiconductor, after these materials are combined with sulphur, the electric conductivity of whole composite is poor, for electrode material, is
One obvious shortcoming.Moreover, transition metal oxide density is larger, easily crystallization, so as to be difficult to prepare high-specific surface area
Material, in addition to extremely individual other special case, the specific surface area for the most of transition metal oxide material reported is both less than
500m2/ g, relatively low specific surface area is unfavorable for a large amount of many sulphions of absorption, so as to limit the raising of sulfur content.
Polysulphide polymer is newfound one to birds of the same feather flock together compound in recent years, and it both has higher sulphur as lithium sulphur positive electrode
Content (up to 90%), also can effectively suppress the dissolving of many lithium sulfides.But general polysulphide polymer is all insulator, directly make
It is difficult to give full play to its specific capacity for electrode material.
The content of the invention
It is an object of the invention to overcome prior art it is above-mentioned it is not enough there is provided a kind of polysulphide polymer composite and its
Preparation method, to solve that existing polysulphide polymer is non-conductive and porous carbon is difficult to the technical problem of effectively fixing many lithium sulfides.
Another object of the present invention is to provide a kind of lithium ion cell positive and containing the lithium ion cell positive
Lithium ion battery, to solve, existing capacity of lithium ion battery is not high, the undesirable technical problem of cyclical stability.
In order to realize foregoing invention purpose, there is provided a kind of system of polysulphide polymer composite for an aspect of of the present present invention
Preparation Method, comprises the following steps：
Many mercapto monomers will be contained to be dissolved in solvent, formed and contain many mercapto monomers solution；
It described will be carried out containing many mercapto monomers solution with porous carbon after mixed processing, remove solvent, obtain the first mixture；
First mixture is carried out after mixed processing with the solution containing elemental sulfur, solvent is removed, obtains the second mixing
Thing；
Second mixture is heated described in making containing many mercapto monomers and elemental sulfur progress polymerisation.
There is provided a kind of polysulphide polymer composite for another aspect of the present invention.The polysulphide polymer composite
Prepared and formed by the preparation method of polysulphide polymer composite of the present invention.
There is provided a kind of lithium ion cell positive for another aspect of the present invention.The lithium ion cell positive includes positive pole
Collector and with reference to the positive-active layer on the plus plate current-collecting body surface, the positive electrode contained by positive-active layer is this
Invention polysulphide polymer composite.
There is provided a kind of lithium ion battery for another aspect of the present invention.The lithium ion battery includes positive plate, it is described
Positive plate is lithium ion cell positive of the present invention.
Compared with prior art, polysulphide polymer composite of the present invention and preparation method thereof utilizes the electric conductivity of porous carbon
With pattern diversity, polysulphide polymer is combined with porous carbon in situ.Wherein, porous carbon not only acts as conducting matrix grain and adsorbed many
The effect of lithium sulfide, and be template so that shape of the pattern of polysulphide polymer composite of the present invention with original porous carbon
Looks are basically identical；And polysulphide polymer is both embedding lithium active material, and the energy many lithium sulfides of efficient absorption, along with porous carbon is to more
The suction-operated of lithium sulfide, can effectively suppress the dissolving of many lithium sulfides and improve the cyclical stability of lithium-sulfur cell.In addition, this hair
Bright polysulphide polymer composite material and preparation method thereof ensure that the performance of the polysulphide polymer composite of preparation is stable, and efficiency
Height, reduces financial cost.
Lithium ion cell positive and lithium ion battery of the present invention are polysulphide polymer of the present invention due to contained positive electrode
Composite, therefore, lithium ion cell positive and lithium ion battery of the present invention are during discharge and recharge, and internal resistance is small, and can
Effectively suppress the dissolving of many lithium sulfides, and not only assign lithium ion battery high capacity, but also it is steady with excellent circulation
It is qualitative.
Embodiment
In order that technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only to explain
The present invention, is not intended to limit the present invention.
The quality of each component noted in the disclosure of the embodiment of the present invention not only may refer to the specific of each component and contain
Amount, can also represent the proportionate relationship of quality between each component, therefore, as long as according to specification each component of the embodiment of the present invention
Content is scaled up or reduced within specification of embodiment of the present invention scope of disclosure.Specifically, the embodiment of the present invention
Quality described in specification can be mass unit known to the chemical fields such as μ g, mg, g, kg.It is described
On the one hand, the embodiments of the invention provide a kind of Stability Analysis of Structures, and can the high polysulphide polymer composite of capacity
Preparation method.The preparation method of the polysulphide polymer composite comprises the following steps：
S01：Many mercapto monomers will be contained to be dissolved in solvent, formed and contain many mercapto monomers solution；
S02：It described will be carried out containing many mercapto monomers solution with porous carbon after mixed processing, remove solvent, obtained first and mix
Compound；
S03：First mixture is carried out after mixed processing with the solution containing elemental sulfur, solvent is removed, obtains second
Mixture；
S04：Second mixture is heated described in making containing many mercapto monomers and elemental sulfur progress polymerisation.
Wherein, in above-mentioned steps S01, the organic monomer for forming polysulphide polymer for polymerization containing many mercapto monomers
Compound, such as in one embodiment, it is described containing many mercapto monomers be trithiocyanuric acid, 2,5- dimercaptothiodiazoles, diphenyl disulfide phenol and
At least one of thiophenol of benzene three.Wherein, the molecular structure of trithiocyanuric acid is for following structural formula A, the molecule of diphenyl disulfide phenol
Structure is that for following structural formula B, the molecular structure of the thiophenol of benzene three is for following structural formula C, point of 2,5- dimercaptothiodiazoles
Minor structure is for following structural formula D.
This contains many mercapto monomers can occur polymerisation with elemental sulfur, generate polysulphide polymer.Dissolve this and contain many mercaptos
It can only can dissolve any solvent for containing many mercapto monomers simple substance that the solvent of base monomer simple substance, which can be,.Such as in an embodiment
In, the solvent can be with but not just for tetrahydrofuran.As long as prepare being enabled to containing many mercapto monomers solution concentrations for formation
Mixed uniformly any concentration is realized in S02 steps with porous carbon.Such as it is but dense not just for 16%-50% quality
Degree.
Can any mix place containing many mercapto monomers solution and the mixed processing that porous carbon is carried out in above-mentioned steps S02
Reason mode, as long as enabling to porous carbon dispersed containing many mercapto monomers solution, and causes containing many mercapto monomers solution
Fill to the loose structure of porous carbon within the scope of disclosed by the invention.Such as can with but not just for stirring, ultrasound
The hybrid modes such as processing.In one embodiment, it is described containing many mercapto monomers solution and porous carbon carry out mixed processing be according to containing
The mass ratio of many mercapto monomers and porous carbon is 1:9~3:1 ratio is mixed, by control containing many mercapto monomers with it is porous
The ratio of carbon, realizes the ratio between final polysulphide polymer and porous carbon, so as to improve leading for polysulphide polymer composite
Electrically, structure and cyclical stability, so as to improve its chemical property.In addition, porous carbon not only acts as conducting matrix grain and absorption
The effect of many lithium sulfides, and be template so that the pattern of polysulphide polymer composite of the present invention is with original porous carbon
Pattern is basically identical.
After the mode of the removing solvent after step S02 mixed processings can be heat drying or vacuum drying etc. so that it is molten
Agent is volatilized.Certainly, if do not required preparation efficiency, it would however also be possible to employ the mode of natural drying.
In above-mentioned steps S03, as long as the solution concentration containing elemental sulfur can enable to the first mixture to realize
Any concentration of even mixing.The solvent for dissolving elemental sulfur can dissolve any solvent of the elemental sulfur.The solvent
Can be with but not just for carbon disulfide.
As the mixed processing in step S02, the mixing of the solution of the first mixture and elemental sulfur in step S03
Processing can be any mixed processing mode, as long as porous carbon is enabled to dispersed containing many mercapto monomers solution, and
So that being filled containing many mercapto monomers solution to the loose structure of porous carbon within the scope of disclosed by the invention.Such as can be with
But not just for the hybrid mode such as stirring, ultrasonically treated.In one embodiment, first mixture and the solution containing elemental sulfur
It according to the mass ratio containing many mercapto monomers and porous carbon is 1 to carry out mixed processing to be:9~3:1 ratio is mixed, and is led to
Cross ratio of the control containing many mercapto monomers and elemental sulfur so that fully carry out polymerisation with elemental sulfur containing many mercapto monomers, together
The content of Shi Tigao sulphur, so that polysulphide polymer composite capacity and cyclical stability are improved, so as to improve its electrochemistry
Energy.
After the mode of the removing solvent after step S03 mixed processings can be heat drying or vacuum drying etc. so that it is molten
Agent is volatilized.Certainly, if do not required preparation efficiency, it would however also be possible to employ the mode of natural drying.
In above-mentioned steps S04, because in the second mixture, elemental sulfur is fully contacted with containing many mercapto monomers, therefore, at this
Under the temperature action of heating in step S04, with many mercapto monomers polymerisation occurs for elemental sulfur, gathers so as to generate many sulphur
Compound.In one embodiment, the temperature for heating the polymerisation occurred is 150~350 DEG C.At this temperature, many mercapto monomers
Occur polymerisation with elemental sulfur, occur polymerisation in-situ preparation with many mercapto monomers original position more particularly in porous carbon
Polysulphide polymer, prepares polysulphide polymer composite.The polysulphide polymer of generation is both embedding lithium active material, and can be high
The many lithium sulfides of effect absorption.
Specific elemental sulfur and trithiocyanuric acid many mercapto monomers generation polymerisation formula are as follows, the polysulphide polymer of generation
As shown in following molecular structural formula E：
Therefore, above-mentioned polysulphide polymer composite material and preparation method thereof utilizes the electric conductivity and pattern diversity of porous carbon, will
It is enriched in containing many mercapto monomers and elemental sulfur in porous carbon loose structure, by thermal response so that many mercapto monomers exist with elemental sulfur
Home position polymerization reaction occurs in porous carbon, so as to effectively increase the structural stability of polysulphide polymer composite, Er Qieyou
Play a part of conducting matrix grain in porous carbon and adsorb many lithium sulfides, along with the polysulphide polymer of in-situ polymerization is both that embedding lithium is lived
Property material, and can many lithium sulfides of efficient absorption, it plays synergy with porous carbon, effectively suppresses the dissolving of many lithium sulfides and changes
The cyclical stability of kind lithium-sulfur cell, while assigning polysulphide polymer composite high capacity.In addition, above-mentioned polysulphide polymer
Composite material and preparation method thereof ensure that the performance of the polysulphide polymer composite of preparation is stable, and efficiency high, reduce through
Ji cost.
Correspondingly, the embodiment of the present invention additionally provides polysulphide polymer composite.The polysulphide polymer composite
Using porous carbon as conducting matrix grain, at least polysulphide polymer is combined with the loose structure situ of porous carbon.Wherein, many sulphur polymerizations
Thing is the polymeric reaction product by being carried out containing many mercapto monomers and elemental sulfur.So, polysulphide polymer composite is due to contained
Porous carbon conducting matrix grain and adsorb the effects of many lithium sulfides, along with the polysulphide polymer of in-situ polymerization is both embedding lithium active matter
Matter, and the energy many lithium sulfides of efficient absorption, it plays synergy with porous carbon, effectively suppresses the dissolving of many lithium sulfides and improves lithium
The cyclical stability of sulphur battery, while assigning polysulphide polymer composite high capacity.
On the other hand, above on the basis of polysulphide polymer composite and preparation method thereof, the embodiment of the present invention is also
There is provided a kind of lithium ion cell positive.The lithium ion cell positive includes the necessary part of traditional lithium-ion battery positive pole,
Such as include collector and with reference to the positive-active layer on the plus plate current-collecting body surface.Contain in wherein described positive-active layer
Positive electrode, and the positive electrode is polysulphide polymer composite described above, so, because positive electrode is above
Described polysulphide polymer composite, therefore, positive electrode capacity of the embodiment of the present invention are high, good cycling stability, and active layer
Stability Analysis of Structures.
Another aspect, above on the basis of lithium ion cell positive, the embodiment of the present invention additionally provides a kind of lithium ion
Battery.The lithium ion battery can be the structure of traditional lithium-ion battery or the lithium ion battery of new construction, still
Regardless of the lithium ion battery of structure, its just extremely lithium ion cell positive described above contained.So, the present embodiment
The positive pole of lithium ion battery is due to being lithium ion cell positive of the embodiment of the present invention, therefore, and the present embodiment lithium ion battery has
High specific capacity and stable cycle performance.
In conjunction with instantiation, polysulphide polymer composite of the embodiment of the present invention and preparation method thereof is carried out further
Describe in detail.
1. polysulphide polymer composite embodiment
Embodiment 11
The present embodiment provides a kind of polysulphide polymer composite and preparation method thereof.The polysulphide polymer composite
Prepared according to including the steps：
S11. porous carbon is combined with polymer monomer：1 gram of 2,5- dimercaptothiodiazole is taken to be dissolved in 5 grams of tetrahydrofurans, plus
Enter 1 gram of carbon ball, stirring treats that solvent volatilization is complete, adds the solution of 4 grams of elemental sulfurs and carbon disulfide, and stirring treats that solvent is evaporated completely
Entirely, compound is obtained, it is standby；
S12. polymer monomer in-situ polymerization：Above-mentioned compound is heated to 150 degree of polymerizations, reacts 12 hours natural coolings,
Obtain the composite of polysulphide polymer and porous carbon.
Embodiment 12
The present embodiment provides a kind of polysulphide polymer composite and preparation method thereof.The polysulphide polymer composite
Prepared according to including the steps：
S21. porous carbon is combined with polymer monomer：0.5 gram of diphenyl disulfide phenol and 0.5 gram of thiophenol of benzene three is taken to be dissolved in 5 grams of tetrahydrochysenes
In furans, 3 grams of nanobelts are added, stirring treats that solvent volatilization is complete, adds the solution of 9 grams of elemental sulfurs and carbon disulfide, stir
Treat that solvent volatilization is complete, obtain compound, it is standby；
S22. polymer monomer in-situ polymerization：Above-mentioned compound is heated to 350 degree of polymerizations, reacts 0.5 hour natural cooling,
Obtain the composite of polysulphide polymer and porous carbon.
Embodiment 13
The present embodiment provides a kind of polysulphide polymer composite and preparation method thereof.The polysulphide polymer composite
Prepared according to including the steps：
S31. porous carbon is combined with polymer monomer：Take 1 gram of trithiocyanuric acid to be dissolved in 5 grams of tetrahydrofurans, add 0.3 gram
Hollow carbon sphere, stirring treats that solvent volatilization is complete, adds the solution of 4 grams of elemental sulfurs and carbon disulfide, and stirring treats that solvent is evaporated completely
Entirely, compound is obtained, it is standby；
S32. polymer monomer in-situ polymerization：Above-mentioned compound is heated to 230 degree of polymerizations, reacts 2 hours natural coolings, obtains
The composite of polysulphide polymer and porous carbon.
Embodiment 14
The present embodiment provides a kind of polysulphide polymer composite and preparation method thereof.The polysulphide polymer composite
Prepared according to including the steps：
S41. porous carbon is combined with polymer monomer：Take 3 grams of trithiocyanuric acids to be dissolved in 5 grams of tetrahydrofurans, add 1 gram of carbon
Nanotube, stirring treats that solvent volatilization is complete, adds the solution of 3 grams of elemental sulfurs and carbon disulfide, and stirring treats that solvent volatilization is complete,
Compound is obtained, it is standby；
S42. polymer monomer in-situ polymerization：Above-mentioned compound is heated to 270 degree of polymerizations, reacts 1 hour natural cooling, obtains
The composite of polysulphide polymer and porous carbon.
Embodiment 15
The present embodiment provides a kind of polysulphide polymer composite and preparation method thereof.The polysulphide polymer composite
Prepared according to including the steps：
S51. porous carbon is combined with polymer monomer：1 gram of thiophenol of benzene three is taken to be dissolved in 5 grams of tetrahydrofurans, 9 grams of addition is mesoporous
Carbon, stirring treats that solvent volatilization is complete, adds the solution of 4 grams of elemental sulfurs and carbon disulfide, and stirring is treated that solvent volatilization is complete, must answered
Compound, it is standby；
S52. polymer monomer in-situ polymerization：Above-mentioned compound is heated to 150 degree of polymerizations, reacts 12 hours natural coolings,
Obtain the composite of polysulphide polymer and porous carbon.
Embodiment 16
The present embodiment provides a kind of polysulphide polymer composite and preparation method thereof.The polysulphide polymer composite
Prepared according to including the steps：
S61. porous carbon is combined with polymer monomer：Take 1 gram of trithiocyanuric acid to be dissolved in 20 grams of tetrahydrofurans, add 5 grams
Graphene, stirring treats that solvent volatilization is complete, adds the solution of 9 grams of elemental sulfurs and carbon disulfide, and stirring treats that solvent volatilization is complete,
Compound is obtained, it is standby；
S62. polymer monomer in-situ polymerization：Above-mentioned compound is heated to 300 degree of polymerizations, reacts 0.5 hour natural cooling,
Obtain the composite of polysulphide polymer and porous carbon.
2. lithium ion cell positive and lithium ion battery embodiment
Embodiment 21- embodiments 27
Polysulphide polymer composite, positive electrode, the binding agent that above-described embodiment 11- embodiments 16 are provided are (poly- inclined
PVF), conductive agent (acetylene black) is according to mass ratio 85:10:5 are well mixed, and add solvent and grind to form uniform slurry, scratch
Onto aluminium foil, backlash is dried into diameter 14mm disk, tabletting prepares lithium ion cell positive, after being then separately dried respectively
With being assembled into embodiment 21 to the fastening lithium ionic cell of embodiment 26 to electrode, electrolyte.It is metal lithium sheet wherein to electrode,
Electrolyte is general lithium-sulfur cell electrolyte.
Comparative example 1-6
The positive electrode that comparative example 1-6 lithium ion cell positives and lithium ion battery are used for carbon sulphur composite, its
Preparation method is：The mass ratio of carbon sulphur is 1:4, carbon ball grinds uniform after being mixed with sulphur powder, then makes within 12 hours in 155 degree of insulations
Sulphur melts and is diffused into the duct of carbon ball.All carbon sulphur composites are all prepared according to same technique.Comparative example 1-6 lithiums from
Sub- anode is with lithium ion battery except positive electrode is different, and other are corresponded with embodiment 21-26, such as embodiment
21 carbon balls used, comparative example 1 also uses carbon ball.
Battery correlated performance is tested
The fastening lithium ionic cell that embodiment 21 to embodiment 26 and comparative example 1-6 are provided is respectively in charge-discharge test
Electric current is tested to carry out correlated performance in such as table 1 below under 167mA/g, measures result as shown in respective performances data in table 1 below.
Table 1
From table 1 it follows that polysulphide polymer composite provided in an embodiment of the present invention has high capacity and followed
Ring performance, therefore, the lithium ion battery using polysulphide polymer of embodiment of the present invention composite as positive electrode have high
Specific capacity and first efficiency, but also with excellent cyclical stability.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of polysulphide polymer composite, comprises the following steps：
Many mercapto monomers will be contained to be dissolved in solvent, formed and contain many mercapto monomers solution；
It described will be carried out containing many mercapto monomers solution with porous carbon after mixed processing, remove solvent, obtain the first mixture；
First mixture is carried out after mixed processing with the solution containing elemental sulfur, solvent is removed, obtains the second mixture；
Second mixture is heated described in making containing many mercapto monomers and elemental sulfur progress polymerisation.
2. preparation method according to claim 1, it is characterised in that：The mass ratio containing many mercapto monomers and elemental sulfur
For 1:(1-9).
3. preparation method according to claim 1, it is characterised in that：The mass ratio containing many mercapto monomers and porous carbon
For 1:9~3:1.
4. according to any described preparation methods of claim 1-3, it is characterised in that：Described is three polysulfide cyanogen containing many mercapto monomers
At least one of acid, 2,5- dimercaptothiodiazoles, diphenyl disulfide phenol and the thiophenol of benzene three.
5. preparation method according to claim 4, it is characterised in that：The temperature of the heating is 150~350 DEG C.
6. preparation method according to claim 5, it is characterised in that：The time of the heating is 0.5~12 hour.
7. according to any described preparation method in claim 1-3,5,6, it is characterised in that：The porous carbon is the shape of porous carbon
Looks are at least one of carbon ball, hollow carbon sphere, nanotube, nanobelt, nanometer sheet or other shapes porous carbon.
8. a kind of polysulphide polymer composite, it is characterised in that：The polysulphide polymer composite is according to claim 1-6
Described preparation method is prepared.
9. a kind of lithium ion cell positive, including plus plate current-collecting body and with reference to the positive-active on the plus plate current-collecting body surface
Layer, it is characterised in that：Positive electrode contained by the positive-active layer is the polysulphide polymer composite wood described in claim 8
Material.
10. a kind of lithium ion battery, including positive plate, it is characterised in that：The positive plate is the lithium ion described in claim 9
Anode.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258213A (en) * | 2018-01-05 | 2018-07-06 | 中国科学院金属研究所 | A kind of organic polymer sulphur/nano carbon-base composite material and its application in lithium-sulfur cell |
| CN108607528A (en) * | 2018-05-08 | 2018-10-02 | 东北大学 | A kind of diatomite/sulfide polymer mercury ion adsorbent and preparation method thereof |
| CN109575288A (en) * | 2018-10-23 | 2019-04-05 | 北京航空航天大学 | A kind of polymerised sulphur positive electrode and with its manufactured lithium-sulfur rechargeable battery |
| CN109686976A (en) * | 2018-12-21 | 2019-04-26 | 中南大学 | A kind of fluorine-containing conjugation micropore sulphur copolymer and preparation method thereof and the application as lithium sulfur battery anode material |
| CN117976887A (en) * | 2024-03-28 | 2024-05-03 | 深圳市泰科动力系统有限公司 | High specific capacity disulfide polymer positive electrode material, preparation method thereof and battery |
-
2017
- 2017-05-22 CN CN201710365831.2A patent/CN107293694A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| SHAO-ZHONG ZENG等: "A composite of hollow carbon nanospheres and sulfur-rich polymers for lithium-sulfur batteries", 《JOURNAL OF POWER SOURCES》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108258213A (en) * | 2018-01-05 | 2018-07-06 | 中国科学院金属研究所 | A kind of organic polymer sulphur/nano carbon-base composite material and its application in lithium-sulfur cell |
| CN108258213B (en) * | 2018-01-05 | 2021-04-20 | 中国科学院金属研究所 | Organic polymer sulfur/nano carbon-based composite material and application thereof in lithium-sulfur battery |
| CN108607528A (en) * | 2018-05-08 | 2018-10-02 | 东北大学 | A kind of diatomite/sulfide polymer mercury ion adsorbent and preparation method thereof |
| CN108607528B (en) * | 2018-05-08 | 2021-02-05 | 东北大学 | Diatomite/vulcanized polymer mercury ion adsorption material and preparation method thereof |
| CN109575288A (en) * | 2018-10-23 | 2019-04-05 | 北京航空航天大学 | A kind of polymerised sulphur positive electrode and with its manufactured lithium-sulfur rechargeable battery |
| CN109686976A (en) * | 2018-12-21 | 2019-04-26 | 中南大学 | A kind of fluorine-containing conjugation micropore sulphur copolymer and preparation method thereof and the application as lithium sulfur battery anode material |
| CN117976887A (en) * | 2024-03-28 | 2024-05-03 | 深圳市泰科动力系统有限公司 | High specific capacity disulfide polymer positive electrode material, preparation method thereof and battery |
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Application publication date: 20171024 |