CN107579189A - A kind of MXene organic double compounds film and preparation method thereof and the application as lithium-sulfur cell barrier film - Google Patents
A kind of MXene organic double compounds film and preparation method thereof and the application as lithium-sulfur cell barrier film Download PDFInfo
- Publication number
- CN107579189A CN107579189A CN201710614633.5A CN201710614633A CN107579189A CN 107579189 A CN107579189 A CN 107579189A CN 201710614633 A CN201710614633 A CN 201710614633A CN 107579189 A CN107579189 A CN 107579189A
- Authority
- CN
- China
- Prior art keywords
- lithium
- film
- mxene
- preparation
- sulfur cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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 kind of MXene organic double compounds film and preparation method thereof and the application as lithium-sulfur cell barrier film.This method comprises the following steps：（1）First acid solution and lithium salts are mixed, add Ti3AlC2Powder, stir, centrifuge, dry, obtain two-dimensional material Ti3C2；（2）Polybenzazole precursor liquid solution is obtained into organic polymer films using electrostatic spinning technique；（3）Using the method for vacuum filtration, by two-dimensional material Ti3C2Filter on organic polymer films, and be applied to lithium-sulfur cell barrier film.MXene organic double compound films prepared by the present invention have good mechanical performance, and heat endurance is good to electrolyte wellability, while can effectively suppress the shuttle effect of more lithium sulfides in lithium-sulfur cell cyclic process, so as to improve the cycle life of lithium-sulfur cell.Described preparation method is simple and easy, is advantageous to large-scale industrial production.
Description
Technical field
The present invention relates to lithium-sulfur cell barrier film field, and in particular to a kind of MXene organic double compounds film and its preparation side
Method and the application as lithium-sulfur cell barrier film.
Background technology
The energy is that the basis of national economic development and power, secondary cell receive widely as a kind of new energy
Concern.Especially lithium ion battery, it is successfully applied in a series of portable electric appts such as computer, mobile phone, but it develops
Large-scale energy storage device can not still be met.
The electrode material of lithium-sulfur cell is with its abundant source, higher energy density（2600 Wh /kg）Become after
Another emerging energy after lithium ion battery.But the development of lithium-sulfur cell receives the limitation of its own material, due to discharge and recharge
During, the generation of more lithium sulfides and its shuttle effect between both positive and negative polarity so that the capacity attenuation of lithium-sulfur cell is serious, together
When potential safety hazard be present.Researcher solves this problem using different methods.Nano material is most commonly introduced, is passed through
Its confinement effect suppresses the shuttle of more lithium sulfides, while increases the electric conductivity of positive electrode.Another method is to utilize porous carbon
The traditional barrier film of graphene modified of material or two dimension, suppresses the shuttle of more lithium sulfides by physical and chemical adsorption, improves
The chemical property of lithium-sulfur cell.
Recently, a species grapheme material-MXene is successfully developed, and it has higher electron conduction, hydrophilic
Property is good, and the features such as easily preparation, MXene is applied into electrochemical research, achieves the achievement to attract people's attention.Due in MXene
Titanium atom has strong suction-operated to more lithium sulfides, and therefore, MXene is expected to show in the modification of lithium-sulfur cell more prominent
Application prospect.Meanwhile scientists there has also been breakthrough progress in this field of battery isolating film, wherein polyimides this
Organic polymer film materials, due to being received extensively with high electrolyte wellability, good heat endurance and mechanical performance
General concern.
Here, MXene is combined and develops the complexes membrane material of high stability a kind of by we with polyimides, and is used for
In lithium-sulfur cell barrier film.
The content of the invention
The invention aims to solve the problems, such as at this stage lithium-sulfur cell exist with defect and a kind of electronics electricity is provided
Conductance is high, and electrolyte wellability is good, high MXene organic double compound films of heat endurance and preparation method thereof.It is and its is successful
Applied in lithium-sulfur cell barrier film, because MXene has strong physical and chemical adsorption effect to more lithium sulfides, so as to inhibit
The shuttle of more lithium sulfides, improve the capacity and cycle life of lithium-sulfur cell.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of MXene organic double compounds film, comprises the following steps：
（1）Lithium salts is mixed with acid solution, obtains mixed liquor；Again by Ti3AlC2Powder is added in mixed liquor, is stirred, and is obtained
Uniform liquid；
（2）By step（1）Gained uniform liquid ultrasound, centrifugation, takes supernatant liquor, is dried to obtain two-dimentional Ti3C2（MXene）Powder；
（3）By step（2）Gained two dimension Ti3C2Powder is dissolved in solvent, ultrasonic disperse, obtains uniform Ti3C2Solution；
（4）Dianhydride and diamines are dissolved in polar solvent, obtain PAA solution；Again by PAA solution carry out electrostatic spinning, heat at
Organic film is obtained after reason；
（5）By step（3）In obtained Ti3C2Solution is filtered by vacuum in step（4）On the organic film of gained, it is dried to obtain
MXene organic double compound films.
Further, step（1）In, the lithium salts is one kind in lithium nitrate, lithium sulfate and lithium bromide；The acid solution
For one kind in sulfuric acid and nitric acid；The mass ratio of the lithium salts and acid solution is 1:100~150；The Ti3AlC2Powder quality is
100~200g。
Further, step（1）In, described Ti3AlC2Powder quality is 100 ~ 200g.
Further, step（1）In, the temperature of the stirring is 30 ~ 60 DEG C.
Further, step（2）In, the ultrasonic time is 1 ~ 3h；The rotating speed of the centrifugation is 3000 ~ 6000
Rpm, time are 20 ~ 60 min；The temperature of the drying is 50 ~ 80 DEG C.
Further, step（3）In, described solvent is water, ethanol and N, one kind in N '-dimethyl formamide；Institute
State two-dimentional Ti3C2The mass ratio of powder and solvent is 1:（500~800）.
Further, step（3）In, the ultrasonic time is 1 ~ 3h.
Further, step（4）In, the dianhydride is in pyromellitic acid anhydride, diphenyl ether dianhydride and biphenyl dianhydride
It is a kind of；The diamines is one kind in p-phenylenediamine, o-phenylenediamine, dicyanodiamine and oxamide；The dianhydride and diamines
Mass ratio is（1~1.2）：1.
Further, step（4）In, the polar solvent is NMP（1-METHYLPYRROLIDONE）、DMF（N, N- dimethyl methyl
Acid amides）Or THF（Tetrahydrofuran）/ methanol mixed solvent.
Further, step（4）In, it in the speed that pushes away of spinning device is 0.01 ~ 0.03mm/min that the electrostatic spinning, which is, spinneret
Device is 10 ~ 30kv with receiver voltage, and temperature is 0 ~ 15 DEG C, under conditions of humidity is 5 ~ 20%, spinning film forming.
Further, step（4）In, the heat treatment is under vacuum, to be warming up to 2 ~ 5 DEG C/min speed
300 ~ 350 DEG C are heat-treated 4 ~ 6 hours.
Further, step（5）In, the temperature of the drying is 50 ~ 80 DEG C.
A kind of MXene organic double compounds film as made from the process described above, the MXene organic double compounds film be used as every
It is applied to from film in lithium-sulfur cell.
MXene organic double compounds film is applied in lithium-sulfur cell as barrier film, has high thermal stability, good machine
Tool performance and electrolyte wellability, while improve the cycle life of lithium-sulfur cell.
Compared with prior art, the invention has the advantages that：
1st, two-dimensional material MXene is combined by the present invention with organic polymer films by the method for vacuum filtration first, and is applied
In lithium-sulfur cell barrier film.Prepared MXene organic double compounds film is provided simultaneously with the highly electron conductive of MXene materials, had
The excellent heat endurance of organic polymeric material, mechanical stability and electrolyte wellability.
2nd, MXene organic double compounds membrane material of the invention is applied in lithium-sulfur cell as barrier film, wherein MXene mono-
Aspect can with caused more lithium sulfides in adsorption electrode material charge and discharge process so as to improve the capacity of lithium-sulfur cell, circulation the longevity
Life, while the electron conduction of battery can be lifted；Organic polymer has excellent heat endurance, mechanicalness as substrate
Energy and good electrolyte wellability, greatly improve the security performance of battery.
Brief description of the drawings
Fig. 1 is that the SEM of MXene organic double compounds film made from embodiment 1 schemes；
Fig. 2 is the Ti of embodiment 23AlC2Powder, two-dimentional Ti3C2The XRD of powder, MXene organic double compound films；
Fig. 3 is that MXene organic double compounds film made from embodiment 3 is applied to lithium-sulfur cell, the cycle performance under 0.5C multiplying powers
Figure.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is further elaborated, but the present invention is not limited to this.
Embodiment 1
（1）The sulfuric acid solution for taking 1g lithium nitrates and 100g concentration to be 18.4mol/L mixes, then by 100g business Ti3AlC2Powder
It is added in above-mentioned solution, is stirred at 30 DEG C；
（2）By step（1）Resulting solution ultrasound 1h, 20min is centrifuged in the case where rotating speed is 3000rpm, takes supernatant liquor, 50 DEG C of dryings
Obtain two-dimentional Ti3C2（MXene）Powder；
（3）By above-mentioned Ti3C2Powder takes 1g to be dissolved in 500g deionized water, ultrasonic 1h, obtains uniform Ti3C2Solution；
（4）1.2g pyromellitic acid anhydrides and 1g p-phenylenediamine are dissolved in NMP at 0 DEG C, PAA solution is obtained, in spinneret
The speed that pushes away of device is 0.01mm/min, and spinning device is 10kv with receiver voltage, and temperature is 10 DEG C, under conditions of humidity is 5%, is entered
Row spinning, 300 DEG C are warming up to 2 DEG C/min speed, heat treatment obtains organic film after 4 hours；
（5）By step（3）In obtained Ti3C2Solution is filtered by vacuum over an organic film, and 50 DEG C are dried to obtain MXene organic composites
Thing film.The complexes membrane is heat-treated 1 hour at 300 DEG C, remains in that original size, obvious thermal contraction does not occur, says
The bright material heat-resistant stability is good；
（6）Using 0.100g sublimed sulfurs as active material, 0.012g conductive blacks are conductive agent, and 0.16g Kynoar is bonding
Agent, three kinds of materials are well mixed, coated on positive pole is used as on aluminium foil, using lithium piece as negative pole, with step（5）The MXene of gained
For organic double compound film as barrier film, glycol dimethyl ether is electrolyte, and lithium-sulfur cell is assembled in argon gas glove box.This implementation
Discharge capacity is 1150 mAh/g to the lithium-sulfur cell of example first under 0.1C multiplying powers, weekly capacity attenuation 2% or so.
The SEM figures of MXene organic double compounds membrane material made from the present embodiment are as shown in Figure 1.
Embodiment 2
（1）It is that 18.4mol/L sulfuric acid solutions mix to take 1g lithium sulfates and 120g concentration, then by 150g business Ti3AlC2Powder adds
Enter into above-mentioned solution, stirred at 40 DEG C；
（2）By step（1）Resulting solution ultrasound 2h, 20min is centrifuged in the case where rotating speed is 4000rpm, takes supernatant liquor, 60 DEG C of dryings
Obtain two-dimentional Ti3C2（MXene）Powder；
（3）By above-mentioned Ti3C2Powder takes 1g to be dissolved in 600g ethanol, ultrasonic 2h, obtains uniform Ti3C2Solution；
（4）1.1g pyromellitic acid anhydrides and 1g p-phenylenediamine are dissolved in DMF at 0 DEG C, PAA solution is obtained, in spinneret
The speed that pushes away of device is 0.02mm/min, and spinning device is 15kv with receiver voltage, and temperature is 15 DEG C, under conditions of humidity is 10%, is entered
Row spinning, 300 DEG C are warming up to 5 DEG C/min speed, organic film is obtained after being heat-treated 5h；
（5）By step（3）In obtained Ti3C2Solution is filtered by vacuum over an organic film, and 60 DEG C are dried to obtain MXene organic composites
Thing film.The complexes membrane has good flexibility, can be stretched, folded, distorted, good mechanical stability；
（6）Using 0.100g sublimed sulfurs as active material, 0.012g conductive blacks are conductive agent, and 0.16g Kynoar is bonding
Agent, three kinds of materials are well mixed, coated on positive pole is used as on aluminium foil, using lithium piece as negative pole, with step（5）The MXene of gained
For organic double compound film as barrier film, glycol dimethyl ether is electrolyte, and lithium-sulfur cell is assembled in argon gas glove box.This implementation
Discharge capacity is 1100 mAh/g to the lithium-sulfur cell of example first under 0.1C multiplying powers, weekly capacity attenuation 3% or so.
The Ti of the present embodiment3AlC2Powder, two-dimentional Ti3C2Powder（Ti3C2Tx）, MXene organic double compound films XRD such as
Shown in Fig. 2.
Embodiment 3
（1）It is that 16mol/L salpeter solutions mix to take 1g lithium bromides and 150g concentration, then by 200g business Ti3AlC2Powder adds
Into above-mentioned solution, stirred at 50 DEG C；
（2）By step（1）Resulting solution ultrasound 3h, 30min is centrifuged in the case where rotating speed is 5000rpm, takes supernatant liquor, 60 DEG C of dryings
Obtain two-dimentional Ti3C2（MXene）Powder；
（3）By above-mentioned Ti3C2Powder takes 1g to be dissolved in 700g deionized water, ultrasonic 3h, obtains uniform Ti3C2Solution；
（4）1.2g pyromellitic acid anhydrides and 1g p-phenylenediamine are dissolved in volume ratio as 1 at 0 DEG C:1 THF/ methanol mixing
In solvent, PAA solution is obtained, is 0.03mm/min, spinning device and the condition that receiver voltage is 30kv in the speed that pushes away of spinning device
Under, temperature is 0 DEG C, and humidity carries out spinning under conditions of being 20%, is obtained after being warming up to 350 DEG C of heat treatment 6h with 2 DEG C/min speed
To organic film；
（5）By step（3）In obtained Ti3C2Solution is filtered by vacuum over an organic film, and 80 DEG C are dried to obtain MXene organic composites
Thing film.The electrolyte of the complexes membrane holds rate and is up to 200%, there is good wellability to electrolyte；
（6）Using 0.100g sublimed sulfurs as active material, 0.012g conductive blacks are conductive agent, and 0.16g Kynoar is bonding
Agent, three kinds of materials are well mixed, coated on positive pole is used as on aluminium foil, using lithium piece as negative pole, with step（5）The MXene of gained
For organic double compound film as barrier film, glycol dimethyl ether is electrolyte, and lithium-sulfur cell is assembled in argon gas glove box.This implementation
Discharge capacity is 808mAh/g to the lithium-sulfur cell of example first under 0.5C multiplying powers, weekly capacity attenuation 1% or so.
The performance map that MXene organic double compounds film made from the present embodiment is applied to lithium-sulfur cell is as shown in Figure 3.
Claims (10)
1. a kind of preparation method of MXene organic double compounds film, it is characterised in that comprise the following steps：
（1）Lithium salts is mixed with acid solution, obtains mixed liquor；Again by Ti3AlC2Powder is added in mixed liquor, is stirred, and is obtained
Even liquid；
（2）By step（1）Gained uniform liquid ultrasound, centrifugation, takes supernatant liquor, dries, obtains two-dimentional Ti3C2Powder；
（3）By step（2）Gained two dimension Ti3C2Powder is dissolved in solvent, ultrasonic disperse, obtains uniform Ti3C2Solution；
（4）Dianhydride and diamines are dissolved in polar solvent, obtain PAA solution；Again by PAA solution carry out electrostatic spinning, heat at
Organic film is obtained after reason；
（5）By step（3）In obtained Ti3C2Solution is filtered by vacuum in step（4）On the organic film of gained, MXene is dried to obtain
Organic double compound film.
2. preparation method according to claim 1, it is characterised in that step（1）In, the lithium salts is lithium nitrate, sulfuric acid
One kind in lithium and lithium bromide；The acid solution is one kind in sulfuric acid and nitric acid；The mass ratio of the lithium salts and acid solution is
1:（100~150）.
3. preparation method according to claim 1, it is characterised in that step（1）In, the temperature of the stirring is 30 ~ 60
℃。
4. preparation method according to claim 1, it is characterised in that step（2）In, the ultrasonic time is 1 ~ 3h；
The rotating speed of the centrifugation is 3000 ~ 6000 rpm, and the time of centrifugation is 20 ~ 60 min；The temperature of the drying is 50 ~ 80 DEG C.
5. preparation method according to claim 1, it is characterised in that step（3）In, described solvent be water, ethanol and
N, one kind in N '-dimethyl formamide；The two-dimentional Ti3C2The mass ratio of powder and solvent is 1:（500~800）.
6. preparation method according to claim 1, it is characterised in that step（4）In, the dianhydride is Pyromellitic Acid two
One kind in acid anhydride, diphenyl ether dianhydride and biphenyl dianhydride；The diamines is p-phenylenediamine, o-phenylenediamine, dicyanodiamine and oxalyl two
One kind in amine；The mass ratio of the dianhydride and diamines is（1~1.2）：1；The polar solvent be NMP, DMF or tetrahydrofuran/
Methanol mixed solvent.
7. preparation method according to claim 1, it is characterised in that step（4）In, the electrostatic spinning is in spinneret
The speed that pushes away of device is 0.01 ~ 0.03mm/min, and spinning device be 10 ~ 30kv with receiver voltage, and temperature is 0 ~ 15 DEG C, humidity for 5 ~
Under conditions of 20%, spinning film forming.
8. preparation method according to claim 1, it is characterised in that step（4）In, the heat treatment is in vacuum condition
Under, it is warming up to 300 ~ 350 DEG C with 2 ~ 5 DEG C/min speed and is heat-treated 4 ~ 6 hours.
A kind of 9. MXene organic double compounds film as made from the method described in claim any one of 1-8.
10. a kind of MXene organic double compounds film described in claim 9 is applied in lithium-sulfur cell as barrier film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710614633.5A CN107579189A (en) | 2017-07-25 | 2017-07-25 | A kind of MXene organic double compounds film and preparation method thereof and the application as lithium-sulfur cell barrier film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710614633.5A CN107579189A (en) | 2017-07-25 | 2017-07-25 | A kind of MXene organic double compounds film and preparation method thereof and the application as lithium-sulfur cell barrier film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107579189A true CN107579189A (en) | 2018-01-12 |
Family
ID=61034069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710614633.5A Pending CN107579189A (en) | 2017-07-25 | 2017-07-25 | A kind of MXene organic double compounds film and preparation method thereof and the application as lithium-sulfur cell barrier film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107579189A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108493502A (en) * | 2018-04-13 | 2018-09-04 | 深圳市得朗高科技有限公司 | A kind of double charcoals and the double poles MXene ion heavy-duty batteries |
| CN109728235A (en) * | 2019-01-22 | 2019-05-07 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | A kind of lithium-sulfur cell polypropylene modification diaphragm and preparation method thereof |
| CN110158238A (en) * | 2018-03-28 | 2019-08-23 | 山东佳星环保科技有限公司 | A kind of preparation method of graphene nanocomposite material |
| CN110247005A (en) * | 2019-05-28 | 2019-09-17 | 浙江大学 | A kind of preparation method of the difunctional composite diaphragm for lithium-sulfur cell |
| CN110350128A (en) * | 2019-06-17 | 2019-10-18 | 浙江大学衢州研究院 | A kind of preparation method of the composite diaphragm for lithium-sulfur cell |
| CN110615438A (en) * | 2018-10-10 | 2019-12-27 | 西南交通大学 | Ti3C2Method for preparing powder |
| CN110729441A (en) * | 2019-10-17 | 2020-01-24 | 广东工业大学 | MXene/polyimide composite battery diaphragm and preparation method and application thereof |
| CN111370629A (en) * | 2020-02-27 | 2020-07-03 | 肇庆市华师大光电产业研究院 | Preparation method of self-supporting functional interlayer of lithium-sulfur battery |
| CN111484085A (en) * | 2020-03-17 | 2020-08-04 | 肇庆市华师大光电产业研究院 | Preparation method of functional interlayer for lithium-sulfur battery and functional interlayer obtained according to preparation method |
| CN112864527A (en) * | 2021-04-02 | 2021-05-28 | 衢州德联环保科技有限公司 | Preparation method of Mxene/PVDF lithium-sulfur battery diaphragm |
| CN113948816A (en) * | 2021-10-18 | 2022-01-18 | 江苏厚生新能源科技有限公司 | MXene composite material modified diaphragm for lithium-sulfur battery and preparation method thereof |
| CN114023963A (en) * | 2021-10-26 | 2022-02-08 | 陕西科技大学 | MXene @ TiS2-TiO2Flexible composite film and preparation method thereof |
| CN114370961A (en) * | 2021-12-31 | 2022-04-19 | 上海工程技术大学 | MXene-GO/adhesive tape composite Janus structure, preparation and application thereof |
| CN114865226A (en) * | 2022-05-25 | 2022-08-05 | 齐齐哈尔大学 | Preparation method and application of MXene-based inorganic particle/PVDF-based polymer composite diaphragm |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974828A (en) * | 2010-09-30 | 2011-02-16 | 江西先材纳米纤维科技有限公司 | Copolymerized polyimide nanofiber nonwoven and preparation method and application thereof |
| CN102251307A (en) * | 2011-05-30 | 2011-11-23 | 中国科学院青岛生物能源与过程研究所 | Polyimide-base nano fibrous membrane, and preparation method and application thereof |
-
2017
- 2017-07-25 CN CN201710614633.5A patent/CN107579189A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101974828A (en) * | 2010-09-30 | 2011-02-16 | 江西先材纳米纤维科技有限公司 | Copolymerized polyimide nanofiber nonwoven and preparation method and application thereof |
| CN102251307A (en) * | 2011-05-30 | 2011-11-23 | 中国科学院青岛生物能源与过程研究所 | Polyimide-base nano fibrous membrane, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIANJUN SONG等: "Immobilizing Polysulfides with MXene-Functionalized Separators for Stable Lithium-Sulfur Batteries", 《APPLIED MATERIALS & INTERFACES》 * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110158238A (en) * | 2018-03-28 | 2019-08-23 | 山东佳星环保科技有限公司 | A kind of preparation method of graphene nanocomposite material |
| CN108493502A (en) * | 2018-04-13 | 2018-09-04 | 深圳市得朗高科技有限公司 | A kind of double charcoals and the double poles MXene ion heavy-duty batteries |
| CN110615438A (en) * | 2018-10-10 | 2019-12-27 | 西南交通大学 | Ti3C2Method for preparing powder |
| CN109728235A (en) * | 2019-01-22 | 2019-05-07 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | A kind of lithium-sulfur cell polypropylene modification diaphragm and preparation method thereof |
| CN110247005A (en) * | 2019-05-28 | 2019-09-17 | 浙江大学 | A kind of preparation method of the difunctional composite diaphragm for lithium-sulfur cell |
| CN110247005B (en) * | 2019-05-28 | 2020-11-13 | 浙江大学 | Preparation method of difunctional composite diaphragm for lithium-sulfur battery |
| CN110350128B (en) * | 2019-06-17 | 2021-11-30 | 浙江大学衢州研究院 | Preparation method of composite diaphragm for lithium-sulfur battery |
| CN110350128A (en) * | 2019-06-17 | 2019-10-18 | 浙江大学衢州研究院 | A kind of preparation method of the composite diaphragm for lithium-sulfur cell |
| CN110729441A (en) * | 2019-10-17 | 2020-01-24 | 广东工业大学 | MXene/polyimide composite battery diaphragm and preparation method and application thereof |
| CN111370629A (en) * | 2020-02-27 | 2020-07-03 | 肇庆市华师大光电产业研究院 | Preparation method of self-supporting functional interlayer of lithium-sulfur battery |
| CN111484085A (en) * | 2020-03-17 | 2020-08-04 | 肇庆市华师大光电产业研究院 | Preparation method of functional interlayer for lithium-sulfur battery and functional interlayer obtained according to preparation method |
| CN112864527A (en) * | 2021-04-02 | 2021-05-28 | 衢州德联环保科技有限公司 | Preparation method of Mxene/PVDF lithium-sulfur battery diaphragm |
| CN113948816A (en) * | 2021-10-18 | 2022-01-18 | 江苏厚生新能源科技有限公司 | MXene composite material modified diaphragm for lithium-sulfur battery and preparation method thereof |
| CN114023963A (en) * | 2021-10-26 | 2022-02-08 | 陕西科技大学 | MXene @ TiS2-TiO2Flexible composite film and preparation method thereof |
| CN114370961A (en) * | 2021-12-31 | 2022-04-19 | 上海工程技术大学 | MXene-GO/adhesive tape composite Janus structure, preparation and application thereof |
| CN114865226A (en) * | 2022-05-25 | 2022-08-05 | 齐齐哈尔大学 | Preparation method and application of MXene-based inorganic particle/PVDF-based polymer composite diaphragm |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107579189A (en) | A kind of MXene organic double compounds film and preparation method thereof and the application as lithium-sulfur cell barrier film | |
| CN107611406B (en) | Preparation method of silicon/graphene/carbon composite negative electrode material | |
| JP6445585B2 (en) | Porous carbon nanotube microspheres and production method and use thereof, metallic lithium-skeleton carbon composite material and production method thereof, negative electrode, and battery | |
| CN102299326B (en) | Graphene modified lithium iron phosphate/carbon composite material and its application | |
| WO2013097553A1 (en) | Lithium ion battery composite electrode material immersed and coated by conducting polymer and preparation method thereof | |
| CN105226285B (en) | A kind of porous Si-C composite material and preparation method thereof | |
| CN104085877A (en) | Porous carbon electrode material based on chitosan and derivative of chitosan thereof as well as preparation method and application of porous carbon electrode material | |
| CN103165894B (en) | Graphene-hydroxyl lithium composite and its preparation method and application | |
| CN104064735A (en) | Lithium titanate-graphene-carbon nanotube composite material and preparation method and application thereof | |
| CN107331839A (en) | A kind of preparation method of carbon nanotube loaded nano titanium oxide | |
| CN109461906B (en) | Preparation method of lithium-sulfur battery positive electrode material | |
| CN103515587A (en) | Preparation methods of lithium titanate-graphene composite material and lithium ion battery | |
| CN103560019B (en) | A kind of zinc ion hybrid super capacitor | |
| CN112038635B (en) | Lithium-sulfur battery graphene-loaded cementite particle composite positive electrode material and preparation method thereof | |
| JP2023526525A (en) | SEPARATOR FOR ELECTROCHEMICAL DEVICE AND MANUFACTURING METHOD THEREOF | |
| CN108288708A (en) | A kind of graphene In-situ reaction phosphoric acid ferrimanganic nickel lithium anode material and preparation method thereof | |
| CN110783564A (en) | Nitrogen-doped carbon-coated ternary positive electrode material and preparation method thereof | |
| CN103022463B (en) | Manganese-based compound cathode material of lithium battery and preparation method of material | |
| CN103545109A (en) | Graphene composite material, preparation method thereof and lithium ion capacitor | |
| CN103456937A (en) | Preparation methods of lithium titanate-graphene composite material and lithium ion battery | |
| CN103413917B (en) | The preparation method of the lithium manganate cathode pole piece containing Graphene | |
| WO2017197675A1 (en) | Lithium titanate-modified material and manufacturing method thereof | |
| CN114520328B (en) | Lithium ion battery negative electrode material, preparation method thereof, negative electrode and battery | |
| CN106450228A (en) | Composite nanometer material for lithium ion battery and preparing method thereof | |
| CN108117056A (en) | The preparation method of graphene coated plasma modification carbonaceous mesophase spherules |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180112 |