CN110592807B - Thin film material for inhibiting growth of lithium dendrite and preparation method thereof - Google Patents
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 210000001787 dendrite Anatomy 0.000 title claims abstract description 34
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 16
- 239000010409 thin film Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 28
- GIWQSPITLQVMSG-UHFFFAOYSA-N 1,2-dimethylimidazole Chemical compound CC1=NC=CN1C GIWQSPITLQVMSG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010408 film Substances 0.000 claims abstract description 22
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 19
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000011241 protective layer Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010923 batch production Methods 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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Abstract
The invention discloses a film material for inhibiting the growth of lithium dendrites and a preparation method thereof, wherein a certain amount of 1, 2-dimethyl imidazole and a proper amount of polyacrylonitrile are dissolved in N, N-dimethylformamide with a certain volume and stirred to obtain a light yellow mixture solution precursor; then electrostatic spinning is carried out under certain voltage, flow rate and relative humidity, and the dried spinning product is soaked in Co-containing solution in sequence2+The ionic methanol solution is soaked in the methanol solution containing 1, 2-dimethyl imidazole, and then the ionic methanol solution is sintered in a tubular furnace in nitrogen atmosphere to obtain a thin film material capable of growing lithium dendrites, so that the cycle service life and the safety of the lithium battery are improved. In the whole preparation process of the material, the operation is simple, the raw material cost is low, the equipment investment is low, and the method is suitable for batch production.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a thin film material for inhibiting growth of lithium dendrites in a lithium battery and a preparation method thereof.
Background
Metallic lithium is currently known as the lowest density metallic material and has a high theoretical specific capacity (3840 mAh/g). Furthermore, Li compares to a standard hydrogen electrode+The redox couple of Li provides the lowest redox potential (-3.04V), which allows the lithium ion secondary battery to have a higher operating voltage during use (Bruce P G et al, Nature Materials,2012,11(1): 19-29; Jung J W et al, Journal of Materials Chemistry A,2016,4(3): 703-750; Xu J J J et al, Energy)&Environmental Science,2014,7(7): 2213-2219). The excellent properties described above have led to the widespread interest of researchers in metallic lithium. However, the lithium metal negative electrode still faces many difficulties in practical application, and the main difficulties include the following three aspects: firstly, the complex reaction on the interface of the lithium metal cathode and the electrolyte leads to the continuous increase of interface impedance, thereby reducing the cycle efficiency in the charge-discharge cycle process; secondly, the number of the circulating circles is continuously increasedThe lithium metal is repeatedly subjected to intercalation and deintercalation reactions, and a lithium negative electrode can generate a serious volume expansion effect to cause the falling of a negative electrode active substance, so that the cycle efficiency of the battery is reduced; thirdly, a large amount of lithium dendrites are formed on the surface of a negative electrode due to the uneven deposition of metal lithium on the surface of the electrode, and the lithium dendrites fall off from the electrode and enter electrolyte to form 'dead lithium', so that the loss of electrode active substances is caused; if the lithium dendrites continue to grow and penetrate through the battery separator to contact the positive electrode, the battery is short-circuited, and the battery may be burnt or even exploded (Xu W et al Energy)&Environmental Science,2014,7(2): 513-; zhamu A et al Energy&Environmental Science,2012,5(2): 5701-; brandt K et al, Solid State Ionics,1994,69(3-4): 173-183). In order to solve the above-mentioned challenges, dendrite growth inhibition methods have been studied from different angles, and studies have found that the three-dimensional structure material can inhibit the growth of dendrites. In 2017, guoshihua proposed a method for suppressing the generation of lithium dendrites on the surface of lithium metal (a method for suppressing the generation of lithium dendrites on the surface of lithium metal, publication No. CN 108063241A). In 2015, Yang et al prepared a three-dimensional copper foil with a micro-skeleton structure by a reduction method, which effectively inhibited the growth of lithium dendrites (Nature Communications,2015,6: 7436). In 2017, Li et al directly inserted metallic lithium into a three-dimensional copper mesh to prepare a lithium metal negative electrode with a three-dimensional structure for suppressing the formation and growth of lithium dendrites (Li Q et al, Advanced Functional Materials,2017,27(18): 1606422). Although the methods have made certain progress or breakthrough, all of them have certain disadvantages or limitations, such as poor lithium affinity, and the inability to induce uniform nucleation of lithium.
The metal organic framework compound contains abundant organic ligands and metal central ions, has a controllable pore channel structure and a larger specific surface area, has strong affinity with lithium due to the abundant reaction sites, and can effectively capture lithium ions. In 2011, Schaefer et al discovered that MOFs Materials as negative electrodes could maintain stable structures during charging and discharging (J L Schaefer et al, Journal of Materials Chemistry,2013,25: 834-839). 2018, wanhao et al prepared a material for inhibiting the growth of lithium dendrites by using ZIF-8 porous carbon (a negative electrode of a lithium battery for inhibiting the growth of lithium dendrites by using a ZIF-8 porous carbon material, publication No. CN 108258241A). It can be seen that the organometallic framework material has certain advantages in inhibiting lithium dendrite deposition on the electrode. In order to realize the inhibition of the growth of lithium dendrites, the invention adopts the electrostatic spinning technology combined with high-temperature sintering to prepare a thin film material based on a metal organic framework derivative, which is used for inhibiting the growth of the lithium dendrites in a lithium battery.
Disclosure of Invention
The invention aims to solve the technical problem of providing a thin film material for inhibiting the growth of lithium dendrites and a preparation method thereof aiming at the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: a process for preparing the film material to suppress the growth of Li dendrite includes such steps as preparing the electrostatic spinning product from 1, 2-dimethyl imidazole as raw material, adding high-molecular polyacrylonitrile as adhesive, electrostatic spinning under high voltage, and sequentially immersing in Co2+Ionic methanol solution and methanol solution of 1, 2-dimethyl imidazole for a certain time and repeating for three times, then taking out and drying, and then adding N2Performing high-temperature sintering in an atmosphere by using a tube furnace to obtain a thin film material for inhibiting the growth of lithium dendrites based on a metal organic framework derivative structure, which specifically comprises the following steps:
1) weighing a certain amount of 1, 2-dimethyl imidazole (C)5H8N2) Dissolving in N, N-Dimethylformamide (DMF) with a certain volume, adding a proper amount of Polyacrylonitrile (PAN), and stirring for 2h to obtain a light yellow mixture solution precursor;
2) performing electrostatic spinning on the faint yellow mixture solution precursor under the conditions of 18-20 kV voltage, 0.7-0.9 mL/h flow rate and 35-45% relative humidity, and drying the obtained electrostatic spinning product at 80 ℃;
3) weighing a certain amount of 1, 2-dimethyl imidazole (C)5H8N2) Dissolving in a certain volume of methanol to prepare a solution A; in addition, a certain amount of cobalt acetate tetrahydrate (Co (Ac)2·4H2O) is dissolved in a certain volume of methanol to prepare a solution B,
4) immersing the dried electrostatic spinning product obtained in step 2) in a solution containing Co2+Taking out the ionic methanol solution B after 30min, then soaking the ionic methanol solution B in a methanol solution A containing 1, 2-dimethyl imidazole for 3h, then taking out the ionic methanol solution B, sequentially repeating the soaking for three times, then taking out and drying the ionic methanol solution B to obtain a purple fiber membrane material;
5) placing the purple fiber film material in a crucible, and then placing the crucible in a tube furnace N2Sintering for 1-3 h at 550-750 ℃, and then naturally cooling to room temperature to obtain a thin film material for inhibiting the growth of lithium dendrites;
the concentration of 1, 2-dimethyl imidazole in the DMF solution is 0.05-0.1 mmol/mL;
the concentration of polyacrylonitrile in the DMF solution is 0.1-0.2 g/mL;
the concentration of 1, 2-dimethyl imidazole in the solution A is 0.1-0.3 mmol/mL;
co in the solution B2+The ion concentration is 0.1-0.2 mmol/mL;
the thin film material prepared by the invention can effectively inhibit the growth of lithium dendrites in the lithium battery, thereby prolonging the cycle service life and improving the safety of the lithium battery.
Compared with the prior art, the invention has the following characteristics:
the 1, 2-dimethyl imidazole ligand in the film material prepared by the invention can form a specific bonding effect with lithium ions, and has an important influence on the deposition of lithium on the surface of an electrode; the surface of the film material is attached with a large number of cobalt and 1, 2-dimethyl imidazole complex particles, the complex particles are provided with micropores and can provide a certain space for the storage or inhabitation of lithium ions, and the higher specific surface energy of the complex particles also has a certain adsorption effect on the ions, so that the deposition of the ions and the growth of lithium dendrites are influenced; at 0.5mA cm-2In this case, cycling through 950h, the cell voltage remained steady (fig. 3), lithium was deposited uniformly on the electrode, and lithium dendrite growth was inhibited.
Drawings
FIG. 1 is an XPS plot of a thin film material made according to the present invention;
FIG. 2 is an SEM image of a thin film material prepared by the present invention;
FIG. 3 is a charge-discharge cycle chart of the battery using the thin film material prepared by the present invention as an electrode protection layer material;
fig. 4 is a view showing charge and discharge cycles of the battery without using the thin film material of the present invention as an electrode protection layer material.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
1.0mmol (0.0961g) of 1, 2-dimethylimidazole (C) was weighed5H8N2) Dissolving in 20mL of N, N-Dimethylformamide (DMF), then adding 2.0g of PAN (polyacrylonitrile), and stirring for 2h to obtain a light yellow mixture solution precursor; performing electrostatic spinning on the yellowish mixture solution precursor under the conditions of 18kV voltage, 0.7mL/h flow rate and 35% relative humidity; drying the obtained electrostatic spinning product at 80 ℃;
3.0mmol (0.288g) of 1, 2-dimethylimidazole is weighed and dissolved in 10mL of methanol to prepare solution A; 1.0mmol (0.249g) of cobalt acetate tetrahydrate is weighed and dissolved in 10mL of methanol to prepare a solution B;
soaking the obtained dry electrostatic spinning product in the solution B for 30min, then taking out, then soaking in the solution A for 3h, then taking out, repeating the soaking for three times in sequence, then taking out and drying to obtain a purple fiber film material; and (3) placing the obtained purple fiber film material in a tubular furnace in a nitrogen atmosphere at 550 ℃ for sintering for 3h, and then naturally cooling to room temperature to obtain the film material for inhibiting the growth of lithium dendrites.
The obtained film material was subjected to X-ray photoelectron spectroscopy (XPS) test, and the results showed diffraction peaks of Co, C, N, and O elements (fig. 1); scanning electron microscope tests show that the film is composed of nano fibers, and a large number of particles are attached to the surfaces of the fibers (figure 2); the prepared film is used as a battery electrode protective layer material, and the current density is0.5mA cm-2In this case, the voltage of the battery was stable 950 times during the charge-discharge cycle (fig. 3), indicating that the electrode did not change significantly and lithium dendrite growth was inhibited; without using the film of the invention as a protective layer material, at a current density of 0.5mA cm-2In this case, the charge and discharge cycles of the battery are shown in fig. 4, and the results show that the voltage is significantly increased after 250 cycles, indicating that the conductivity of the electrode is significantly changed, resulting in significant deterioration of the cycle performance of the battery.
Example 2
2.0mmol (0.0961g) of 1, 2-dimethylimidazole (C) was weighed5H8N2) Dissolving in 20mL of N, N-Dimethylformamide (DMF), then adding 4.0g of PAN (polyacrylonitrile), and stirring for 2h to obtain a light yellow mixture solution precursor; performing electrostatic spinning on the yellowish mixture solution precursor under the conditions of 20kV voltage, 0.9mL/h flow rate and relative humidity of 45%; drying the obtained electrostatic spinning product at 80 ℃;
1.0mmol (0.288g) of 1, 2-dimethylimidazole is weighed and dissolved in 10mL of methanol to prepare solution A; weighing 2.0mmol (0.249g) of cobalt acetate tetrahydrate, and dissolving in 10mL of methanol to prepare a solution B;
soaking the obtained dry electrostatic spinning product in the solution B for 30min, then taking out, then soaking in the solution A for 3h, then taking out, repeating the soaking for three times in sequence, then taking out and drying to obtain a purple fiber film material; and (3) placing the obtained purple fiber film material in a tubular furnace in a nitrogen atmosphere at 750 ℃ for sintering for 1h, and then naturally cooling to room temperature to obtain the film material for inhibiting the growth of lithium dendrites. And carrying out test characterization and electrochemical performance test on the obtained film material by XPS and SEM.
Example 3
2.0mmol (0.0961g) of 1, 2-dimethylimidazole (C) was weighed5H8N2) Dissolving in 20mL of N, N-Dimethylformamide (DMF), adding 3.0g of PAN (polyacrylonitrile), and stirring for 2h to obtain a light yellow mixture solution precursor; the precursor of the light yellow mixture solution is subjected to relative reaction under the voltage of 19kV and the flow rate of 0.8mL/hPerforming electrostatic spinning under the atmosphere with the humidity of 40%; drying the obtained electrostatic spinning product at 80 ℃;
weighing 2.0mmol (0.288g) of 1, 2-dimethylimidazole and dissolving in 10mL of methanol to prepare a solution A; weighing 2.0mmol (0.249g) of cobalt acetate tetrahydrate, and dissolving in 10mL of methanol to prepare a solution B;
soaking the obtained dry electrostatic spinning product in the solution B for 30min, then taking out, then soaking in the solution A for 3h, then taking out, repeating the soaking for three times in sequence, then taking out and drying to obtain a purple fiber film material; and (3) placing the purple fiber film material in a tubular furnace in a nitrogen atmosphere at 650 ℃ for sintering for 1.5h, and then naturally cooling to room temperature to obtain the film material for inhibiting the growth of lithium dendrites. And carrying out test characterization and electrochemical performance test on the obtained film material by XPS and SEM.
Claims (2)
1. A preparation method of a thin film material for inhibiting the growth of lithium dendrites is characterized by comprising the following steps:
1) weighing 1, 2-dimethylimidazole, dissolving in DMF (dimethyl formamide), adding polyacrylonitrile, and stirring for 2 hours to obtain a light yellow mixture solution precursor;
2) performing electrostatic spinning on the faint yellow mixture solution precursor under the conditions of 18-20 kV voltage, 0.7-0.9 mL/h flow rate and 35-45% relative humidity, and drying the obtained electrostatic spinning product at 80 ℃;
3) weighing 1, 2-dimethyl imidazole, and dissolving in methanol to prepare a solution A; weighing cobalt acetate tetrahydrate, and dissolving the cobalt acetate tetrahydrate in methanol to prepare a solution B;
4) immersing the dried electrostatic spinning product obtained in step 2) in a solution containing Co2+Taking out the ionic methanol solution B after 30min, then soaking the ionic methanol solution B in a methanol solution A containing 1, 2-dimethyl imidazole for 3h, then taking out the ionic methanol solution B, sequentially repeating the soaking for three times, then taking out and drying the ionic methanol solution B to obtain a purple fiber membrane material;
5) placing the purple fiber film material in a crucible, and then placing the crucible in a tube furnace N2Sintering for 1-3 h at 550-750 ℃, and then naturally cooling to room temperature to obtain a thin film material for inhibiting the growth of lithium dendrites;
the concentration of 1, 2-dimethyl imidazole in the DMF solution is 0.05-0.1 mmol/mL;
the concentration of polyacrylonitrile in the DMF solution is 0.1-0.2 g/mL;
the concentration of 1, 2-dimethyl imidazole in the solution A is 0.1-0.3 mmol/mL;
co in the solution B2+The ion concentration is 0.1 to 0.2 mmol/mL.
2. A thin film material for suppressing lithium dendrite growth prepared by the preparation method of claim 1 wherein the current density is 0.5mA cm-2Under the condition, the film material can inhibit the growth of lithium dendrite in the process of charging and discharging the battery as a protective layer material on the surface of the lithium ion battery electrode, thereby prolonging the cycle service life and improving the safety of the lithium battery.
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| CN115006998A (en) * | 2022-06-16 | 2022-09-06 | 浙江理工大学 | Composite nanofiber membrane for heavy metal sewage treatment and preparation method and application thereof |
Family Cites Families (12)
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| JP2707664B2 (en) * | 1988-12-19 | 1998-02-04 | 松下電器産業株式会社 | Lithium secondary battery |
| JPH06223820A (en) * | 1993-01-21 | 1994-08-12 | Mitsubishi Cable Ind Ltd | Negative electrode for lithium secondary battery |
| US5888666A (en) * | 1996-03-05 | 1999-03-30 | Canon Kabushiki Kaisha | Secondary battery |
| CN103668780B (en) * | 2012-09-26 | 2016-02-03 | 比亚迪股份有限公司 | Polymer film, gel polymer electrolyte and polymer Li-ion battery and preparation method thereof |
| JP2016182817A (en) * | 2015-03-25 | 2016-10-20 | 特種東海製紙株式会社 | Laminate |
| CN108400379B (en) * | 2018-01-17 | 2020-04-03 | 北京大学 | Preparation method of high-safety lithium ion battery diaphragm and preparation of full battery |
| CN108346820A (en) * | 2018-01-19 | 2018-07-31 | 王群华 | A kind of inhibition lithium dendrite growth cobalt acid lithium electrolyte preparation method |
| CN109056194B (en) * | 2018-07-12 | 2021-08-27 | 东华大学 | Flexible lithium lanthanum titanium oxide ceramic nanofiber membrane material and preparation method thereof |
| CN109524598A (en) * | 2018-11-21 | 2019-03-26 | 广东工业大学 | A kind of battery diaphragm and preparation method thereof |
| CN109755446B (en) * | 2018-12-10 | 2021-11-23 | 沈阳化工大学 | Lithium-sulfur battery diaphragm and preparation method thereof |
| CN110034330B (en) * | 2019-04-10 | 2021-05-04 | 华北电力大学 | Preparation method of composite solid electrolyte for lithium/sodium battery |
| CN110190328A (en) * | 2019-05-24 | 2019-08-30 | 力信（江苏）能源科技有限责任公司 | Solid electrolyte material, dielectric film and preparation method thereof |
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