CN113097643A - Modified diaphragm for lithium-sulfur battery and preparation process thereof - Google Patents
Modified diaphragm for lithium-sulfur battery and preparation process thereof Download PDFInfo
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- CN113097643A CN113097643A CN202110336062.XA CN202110336062A CN113097643A CN 113097643 A CN113097643 A CN 113097643A CN 202110336062 A CN202110336062 A CN 202110336062A CN 113097643 A CN113097643 A CN 113097643A
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 44
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 44
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims description 69
- 239000011248 coating agent Substances 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 38
- 239000010410 layer Substances 0.000 claims description 33
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002002 slurry Substances 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 18
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 18
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- 238000000231 atomic layer deposition Methods 0.000 claims description 13
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910001510 metal chloride Inorganic materials 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 abstract description 13
- 239000010941 cobalt Substances 0.000 abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 229920001021 polysulfide Polymers 0.000 abstract description 7
- 239000005077 polysulfide Substances 0.000 abstract description 7
- 150000008117 polysulfides Polymers 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- 230000008021 deposition Effects 0.000 description 10
- 239000012528 membrane Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 238000005137 deposition process Methods 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229940099607 manganese chloride Drugs 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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 modified diaphragm for a lithium-sulfur battery and a preparation process thereof. According to the invention, the composite layer is arranged on the base film and is prepared from the metal sulfide and the metal oxide, the metal sulfide, namely the cobalt octasulfide, is arrayed on the surface of the base film, the metal sulfide has porosity and polarity, and the metal oxide has adsorption and catalytic properties and is compounded, so that the catalytic action of the metal oxide is fully exerted by utilizing the physical barrier and chemical adsorption effects of the metal sulfide, the mechanical stability is improved, the shuttle effect of the polysulfide is effectively prevented, the shuttle effect of the prepared composite layer is inhibited, and the coulomb efficiency and the cycle life of the lithium-sulfur battery are improved.
Description
Technical Field
The invention relates to the technical field of battery diaphragms, in particular to a modified diaphragm for a lithium-sulfur battery and a preparation process thereof.
Background
With the continuous miniaturization of electronic equipment and the rapid development of mobile communication equipment, portable electronic information products, electric automobiles and energy storage power stations, the traditional lithium ion batteries using transition metal oxides such as lithium cobaltate (LiCoO2), lithium manganate (LiMn 2O 4) and lithium nickelate (LiNiO2) as positive electrode materials cannot meet the requirements of overall development, especially cannot meet the requirements of high specific capacity and high energy density. In the prior art, because the lithium-sulfur battery uses metallic lithium as a negative electrode and uses sulfur or a sulfur composite material as a positive electrode, during the charging and discharging processes, elemental sulfur is reduced into long-chain polysulfide Li2 Sx (4 < x < 8), which can migrate when dissolved in electrolyte to cause shuttle effect, and then the elemental sulfur is continuously reduced into short-chain polysulfide, finally insulating and insoluble Li 2S 2/Li 2S is generated, and insoluble Li 2S 2/Li 2S is deposited on the surface of the metallic lithium electrode, which directly causes active substance loss and seriously affects the coulombic efficiency and the cycle life of the battery, finally dendritic lithium generated by uneven dissolution and deposition and volume expansion during the formation process of lithium sulfide can cause rapid attenuation of discharge capacity, the traditional diaphragm is mainly made of polypropylene PP, polyethylene PE or a composite material PP/PE/PP thereof, although these films are inexpensive and highly flexible, they have poor lyophilic properties and low ionic conductivity and cannot suppress the dissolution and diffusion of polysulfides in the electrolyte. Therefore, we propose a modified separator for a lithium-sulfur battery and a preparation process thereof.
Disclosure of Invention
The invention aims to provide a modified diaphragm for a lithium-sulfur battery and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the modified diaphragm for the lithium-sulfur battery comprises a base film and a composite layer arranged on the surface of the base film, wherein the composite layer is doped with nano metal oxide and octa-cobalt sulfide.
Further, the octa-cobalt sulfide is prepared by reacting cobalt nitrate, dimethyl imidazole and sulfur chloride.
Further, the nano metal oxide is Al2O3、RuO2、MnO、CeO2、TiO2One or more of (a).
Further, the base film is a single-layer or multi-layer wet-process separator.
In the technical scheme, a composite layer is arranged on a base membrane prepared by a wet method, the composite layer is prepared from metal sulfide and nano metal oxide, and metal sulfide, namely, cobalt octasulfide and cobalt octasulfide are arrayed on the surface of the base membrane;
wherein, the metal sulfide has porosity and polarity, and can adsorb lithium polysulfide through physical-chemical synergistic action. Compared with the common diaphragm, the cobalt octasulfide array has larger specific surface area, grows on the surface of the base film in situ and has higher mechanical stability, and the cobalt octasulfide has a hollow structure, can effectively prevent shuttle of polysulfide, and simultaneously inhibits the shuttle effect of the lithium polysulfide through double effects of physical barrier and chemical adsorption.
The nano metal oxide has nano size, large specific surface area and good adsorption performance, and can catalyze the reduction reaction. The battery made of the pure metal oxide modified diaphragm has lower discharge capacity, which can cause the energy density of the battery to be lower; the metal oxide is compounded with the cobalt nona octasulfide array as an auxiliary material, the physical barrier and chemical adsorption effects of the metal oxide can be utilized, the catalytic effect of the metal oxide is fully exerted, the shuttle effect of the prepared composite layer is inhibited, and the coulombic efficiency and the cycle life of the lithium-sulfur battery are improved.
A preparation process of a modified diaphragm for a lithium-sulfur battery comprises the following steps:
(1) dissolving cobalt nitrate and dimethyl imidazole in a solvent, reacting until the reaction is finished to form a precursor, and adding a binder to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film to form a precursor coating, and preparing a diaphragm A;
(3) taking a diaphragm A, and depositing a nano metal oxide layer on the surface of the precursor coating by adopting an atomic layer deposition technology to prepare a diaphragm B;
(4) and taking the diaphragm B, and vulcanizing to obtain a composite layer to obtain the modified diaphragm.
Further, the method comprises the following steps:
(1) dissolving cobalt nitrate and dimethyl imidazole in deionized water, reacting at the temperature of 30-80 ℃ for 5-12 h to form a precursor after the reaction is finished, and adding a binder to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at the temperature of 60-80 ℃ for 1-2 h to form a precursor coating to obtain a diaphragm A;
(3) taking a diaphragm A, taking metal chloride and deionized water as reaction sources, depositing on the surface of a precursor coating to form a nano metal oxide layer, and depositing process parameters: the reaction temperature is 40-80 ℃, the period of atomic layer deposition is 20-50 weeks, and a diaphragm B is prepared;
(4) and (3) putting the diaphragm B into a carbon disulfide solution containing 2-5% of sulfur chloride, and vulcanizing to obtain a composite layer, thus obtaining the modified diaphragm.
Further, the molar ratio of the cobalt nitrate to the dimethylimidazole is (1:1) to (1: 3).
Further, the binder is one or a combination of more of styrene butadiene rubber, polyacrylic acid and polyvinylidene fluoride.
In the technical scheme, cobalt nitrate and dimethyl imidazole are reacted to generate dimethyl imidazole cobalt to prepare a precursor of octa-cobalt sulfide, the precursor is mixed with a binder to prepare precursor slurry, the precursor slurry is coated on the surface of a base membrane, and a diaphragm containing a metal framework dimethyl imidazole cobalt (ZIF-67) layer is formed after drying; placing the precursor coating in an atomic deposition instrument, and depositing metal oxide on the surface of the precursor coating by utilizing an atomic layer deposition technology and taking metal chloride and deionized water as reaction sources; the precursor reacts with sulfur chloride to prepare a product of the octa-cobalt sulfide, and the precursor is uniformly dispersed in the precursor slurry, so that the metal sulfide of the octa-cobalt sulfide is distributed on the surface of the diaphragm in an array manner to form a nano metal oxide-octa-cobalt sulfide array modified composite layer, and the technical scheme is realized;
the preparation step of the nano metal oxide is arranged in the preparation step of the metal sulfide, so that the metal sulfide of the cobalt octasulfide can be fully contacted with the nano metal oxide while being attached to the surface of the base film, the synergistic effect of the metal sulfide of the cobalt octasulfide and the nano metal oxide is improved, the coulombic efficiency of the lithium-sulfur battery is improved, and the cycle life of the lithium-sulfur battery is prolonged.
Compared with the prior art, the invention has the following beneficial effects:
according to the modified diaphragm for the lithium-sulfur battery and the preparation process thereof, the composite layer is arranged on the base film and is made of the metal sulfide and the metal oxide, the metal sulfide, namely the cobalt octasulfide, is arrayed on the surface of the base film, the metal sulfide has porosity and polarity, and the metal oxide has adsorption and catalysis properties and is compounded with the metal sulfide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The polyethylene film prepared by the wet process was taken as the base film in the following experiment.
Example 1
(1) Dissolving cobalt nitrate and dimethyl imidazole in deionized water at a molar ratio of 1:1, reacting at 30 ℃ for 5h to form a precursor after the reaction is finished, adding a binder which is styrene butadiene rubber to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at 60 ℃ for 0.5h to form a precursor coating to obtain a diaphragm A;
(3) placing the diaphragm A in an atomic deposition instrument, and depositing on the surface of the precursor coating by taking 0.01mol/L aluminum chloride and deionized water as reaction sources to form a nano metal oxide layer, wherein the nano metal oxide is Al2O3And deposition process parameters are as follows: the reaction temperature is 40 ℃, the period of atomic layer deposition is 20 weeks, and a diaphragm B is prepared;
(4) and (3) putting the diaphragm B into a carbon disulfide solution containing 2% of sulfur chloride, and vulcanizing to obtain a composite layer, thus obtaining the modified diaphragm.
Example 2
(1) Dissolving cobalt nitrate and dimethyl imidazole in deionized water at a molar ratio of 1:1, reacting at 55 ℃ for 8.5h to form a precursor after the reaction is finished, adding a binder, wherein the binder is polyacrylic acid, and preparing precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at 70 ℃ for 1h to form a precursor coating to obtain a diaphragm A;
(3) placing the diaphragm A in an atomic deposition instrument, and depositing on the surface of the precursor coating by taking 0.01mol/L ruthenium chloride and deionized water as reaction sources to form a nano metal oxide layer, wherein the nano metal oxide is RuO2And deposition process parameters are as follows: the reaction temperature is 60 ℃, the period of atomic layer deposition is 35 weeks, and a diaphragm B is prepared;
(4) and (3) putting the diaphragm B into a carbon disulfide solution containing 3.5% of sulfur chloride, and vulcanizing to obtain a composite layer, thus obtaining the modified diaphragm.
Example 3
(1) Dissolving cobalt nitrate and dimethyl imidazole in deionized water at a molar ratio of 1:1, reacting at 80 ℃ for 12h to form a precursor after the reaction is finished, adding a binder which is polyvinylidene fluoride to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at the temperature of 80 ℃ for 1h to form a precursor coating to obtain a diaphragm A;
(3) taking a diaphragm A, placing the diaphragm A in an atomic deposition instrument, depositing on the surface of a precursor coating by taking 0.01mol/L manganese chloride and deionized water as reaction sources to form a nano metal oxide layer, wherein the nano metal oxide is MnO, and the deposition process parameters are as follows: the reaction temperature is 80 ℃, the period of atomic layer deposition is 50 weeks, and a diaphragm B is prepared;
(4) and (3) putting the diaphragm B into a carbon disulfide solution containing 5% of sulfur chloride, and vulcanizing to obtain a composite layer, thus obtaining the modified diaphragm.
Example 4
(1) Dissolving cobalt nitrate and dimethyl imidazole in deionized water at a molar ratio of 1:2, reacting at 80 ℃ for 12h to form a precursor, adding a binder which is styrene butadiene rubber to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at the temperature of 80 ℃ for 1h to form a precursor coating to obtain a diaphragm A;
(3) placing the diaphragm A in an atomic deposition instrument, and depositing on the surface of the precursor coating by using 0.01mol/L cerium chloride and deionized water as reaction sources to form a nano metal oxide layer, wherein the nano metal oxide is CeO2And deposition process parameters are as follows: the reaction temperature is 80 ℃, the period of atomic layer deposition is 50 weeks, and a diaphragm B is prepared;
(4) and (3) putting the diaphragm B into a carbon disulfide solution containing 5% of sulfur chloride, and vulcanizing to obtain a composite layer, thus obtaining the modified diaphragm.
Example 5
(1) Dissolving cobalt nitrate and dimethyl imidazole in deionized water at a molar ratio of 1:3, reacting at 80 ℃ for 12h to form a precursor, adding a binder which is styrene butadiene rubber to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at the temperature of 80 ℃ for 1h to form a precursor coating to obtain a diaphragm A;
(3) placing the diaphragm A in an atomic deposition instrument, and depositing on the surface of the precursor coating by taking 0.01mol/L titanium chloride and deionized water as reaction sources to form a nano metal oxide layer, wherein the nano metal oxide is TiO2And deposition process parameters are as follows: the reaction temperature is 80 ℃, the period of atomic layer deposition is 50 weeks, and a diaphragm B is prepared;
(4) and (3) putting the diaphragm B into a carbon disulfide solution containing 5% of sulfur chloride, and vulcanizing to obtain a composite layer, thus obtaining the modified diaphragm.
Comparative example 1
Taking a base membrane, placing the base membrane in an atomic deposition instrument, depositing on the surface of a precursor coating by taking 0.01mol/L manganese chloride and deionized water as reaction sources to form a nano metal oxide layer, wherein the nano metal oxide is MnO, and the deposition process parameters are as follows: the reaction temperature is 80 ℃, the period of atomic layer deposition is 50 weeks, and the battery diaphragm is prepared.
Comparative example 2
(1) Dissolving cobalt nitrate and dimethyl imidazole in deionized water at a molar ratio of 1:1, reacting at 80 ℃ for 12h to form a precursor, adding a binder which is styrene butadiene rubber to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at the temperature of 80 ℃ for 2h to form a precursor coating to obtain a diaphragm A;
(3) and (3) putting the diaphragm A into a carbon disulfide solution containing 5% of sulfur chloride, and vulcanizing to obtain the modified diaphragm.
Comparative example 3
(1) Dissolving cobalt nitrate and dimethyl imidazole in deionized water at a molar ratio of 1:1, reacting at 80 ℃ for 12h to form a precursor, adding a binder which is styrene butadiene rubber to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at the temperature of 80 ℃ for 2h to form a precursor coating to obtain a diaphragm A;
(3) putting the diaphragm A into a carbon disulfide solution containing 5% of sulfur chloride, and vulcanizing to obtain a diaphragm B;
(4) obtaining a diaphragm B, placing the diaphragm B in an atomic deposition instrument, depositing on the surface of the precursor coating by taking 0.01mol/L manganese chloride and deionized water as reaction sources to form a nano metal oxide layer, wherein the nano metal oxide is MnO, and the deposition process parameters are as follows: the reaction temperature is 80 ℃, the period of atomic layer deposition is 50 weeks, and the membrane modified by the nano metal oxide and the cobalt nonaoctasulfide is obtained, so that the modified membrane is prepared.
Comparative example 4
(1) Taking a base membrane, placing the base membrane in an atomic deposition instrument, depositing on the surface of a precursor coating by taking 0.01mol/L manganese chloride and deionized water as reaction sources to form a nano metal oxide layer, wherein the nano metal oxide is MnO, and the deposition process parameters are as follows: the reaction temperature is 80 ℃, the period of atomic layer deposition is 50 weeks, and the diaphragm modified by the nano metal oxide and the cobalt nonaoctasulfide is obtained, so that the diaphragm A is prepared.
(2) Dissolving cobalt nitrate and dimethyl imidazole in deionized water at a molar ratio of 1:1, reacting at 80 ℃ for 12h to form a precursor, adding a binder which is styrene butadiene rubber to prepare precursor slurry;
(3) coating the precursor slurry on the surface of the diaphragm A, and drying at the temperature of 80 ℃ for 2 hours to form a precursor coating to obtain a diaphragm B;
(4) placing the diaphragm B in a carbon disulfide solution containing 5% of sulfur chloride for vulcanization to prepare a modified diaphragm; comparative example 5
And taking the base film as a battery diaphragm.
Experiment of
The separators obtained in examples 1 to 5 and comparative examples 1 to 5 were charged with 70 wt% of sulfur powder and 15 wt% of ultra-fine powderConductive carbon black, 15 wt% polyvinylidene fluoride as a positive electrode, metal lithium as a negative electrode, and 1.85mol/L LiCF3SO3Preparing lithium sulfur battery by/DOL and DME (volume ratio is 1: 1);
taking the prepared lithium-sulfur battery as a sample, carrying out constant-current charge and discharge under the same current density within the voltage range of 1.8-2.8V, detecting the electrochemical performance of the sample, taking the percentage of the 1 st discharge capacity and the charge capacity of the sample as coulombic efficiency, testing the mass specific capacity and the volume specific capacity of the sample at 1 st, 5 th, 15 th, 50 th, 100 th and 200 th times of circulation, and recording to obtain the following detection results:
from the data in the table above, it is clear that the following conclusions can be drawn:
the separators obtained in examples 1 to 5 were compared with the separators obtained in comparative examples 1 to 5, and the results of the measurements were found to be,
1. compared with the diaphragms obtained in comparative examples 1 to 5, the diaphragms obtained in examples 1 to 5 have higher initial data of specific capacity and area capacity, relatively slow descending trend along with the increase of cycle number and higher coulombic efficiency, which fully shows that the diaphragms prepared by the invention improve the coulombic efficiency and the cycle life of the lithium-sulfur battery;
2. the diaphragms obtained in the embodiments 3 to 5 are compared with each other, coulombic efficiency data, specific capacity and area capacity initial data of the diaphragms are not obviously changed, the descending trend is gradually slowed along with the increase of the cycle number, and the change of the proportion between the cobalt nitrate and the dimethyl imidazole can influence the cycle life of the manufactured battery;
3. the diaphragm obtained in the example 3 is compared with the diaphragms obtained in the comparative examples 1 to 5, the diaphragm obtained in the comparative example 1 is a nano metal oxide modified diaphragm, and the diaphragm obtained in the comparative example 2 is an octa-vulcanized nine-cobalt array modified diaphragm, compared with the diaphragm obtained in the example 3, the specific capacity and area capacity data of the comparative examples 1 to 2 are obviously reduced in circulation, and the coulombic efficiency data are also reduced, so that the prepared lithium-sulfur battery is poorer in coulombic efficiency and cycle life only by utilizing the nano metal oxide or metal sulfide to modify the diaphragm; the modification of the diaphragm under the combined action of the nano metal oxide and the cobalt nona octasulfide is fully demonstrated, and the coulombic efficiency and the cycle life of the lithium-sulfur battery are improved;
comparative example 3 the procedure (3) and the procedure (4) in example 3 were reversed and comparative example 4 the procedure (3) was carried out in advance, and it is clear from the data that the coulombic efficiency and the cycle life of the lithium-sulfur batteries manufactured in comparative examples 3 to 4 were inferior to those of example 3, and it is fully demonstrated that the manufacturing process of the present invention has a positive influence on the coulombic efficiency and the cycle life of the lithium-sulfur batteries manufactured in connection with comparative examples 1 to 2.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A modified diaphragm for a lithium-sulfur battery is characterized in that: the modified diaphragm comprises a base film and a composite layer arranged on the surface of the base film, wherein the composite layer is doped with nano metal oxide and octa-cobalt sulfide.
2. The modified separator for a lithium-sulfur battery according to claim 1, wherein: the octa-cobalt sulfide is prepared by reacting cobalt nitrate, dimethyl imidazole and sulfur chloride.
3. The modified separator for a lithium-sulfur battery according to claim 1, wherein: the nano metal oxide is Al2O3、RuO2、MnO、CeO2、TiO2One or more of (a).
4. The modified separator for a lithium-sulfur battery according to claim 1, wherein: the base film is a single-layer or multi-layer wet-process diaphragm.
5. A preparation process of a modified diaphragm for a lithium-sulfur battery is characterized by comprising the following steps:
(1) dissolving cobalt nitrate and dimethyl imidazole in a solvent, reacting until the reaction is finished to form a precursor, and adding a binder to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film to form a precursor coating, and preparing a diaphragm A;
(3) taking a diaphragm A, and depositing a nano metal oxide layer on the surface of the precursor coating by adopting an atomic layer deposition technology to prepare a diaphragm B;
(4) and taking the diaphragm B, and vulcanizing to obtain a composite layer to obtain the modified diaphragm.
6. The preparation process of the modified diaphragm for the lithium-sulfur battery according to claim 5, characterized by comprising the following steps:
(1) dissolving cobalt nitrate and dimethyl imidazole in deionized water, reacting at the temperature of 30-80 ℃ for 5-12 h to form a precursor after the reaction is finished, and adding a binder to prepare precursor slurry;
(2) coating the precursor slurry on the surface of a base film, and drying at the temperature of 60-80 ℃ for 1-2 h to form a precursor coating to obtain a diaphragm A;
(3) taking a diaphragm A, taking metal chloride and deionized water as reaction sources, depositing on the surface of a precursor coating to form a nano metal oxide layer, and depositing process parameters: the reaction temperature is 40-80 ℃, the period of atomic layer deposition is 20-50 weeks, and a diaphragm B is prepared;
(4) and (3) putting the diaphragm B into a carbon disulfide solution containing 2-5% of sulfur chloride, and vulcanizing to obtain a composite layer, thus obtaining the modified diaphragm.
7. The process according to claim 5, wherein the modified separator is prepared by the following steps: the molar ratio of the cobalt nitrate to the dimethyl imidazole is (1:1) - (1: 3).
8. The process according to claim 5, wherein the modified separator is prepared by the following steps: the binder is one or a combination of more of styrene butadiene rubber, polyacrylic acid and polyvinylidene fluoride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114590842A (en) * | 2021-12-30 | 2022-06-07 | 杭州电子科技大学 | Preparation method of morphology-controllable cobalt nonaoctasulfide material and application of morphology-controllable cobalt nonasulfide material in electrode |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114590842A (en) * | 2021-12-30 | 2022-06-07 | 杭州电子科技大学 | Preparation method of morphology-controllable cobalt nonaoctasulfide material and application of morphology-controllable cobalt nonasulfide material in electrode |
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