CN114361712A - Ternary material functional diaphragm of lithium-sulfur battery and preparation method thereof - Google Patents
Ternary material functional diaphragm of lithium-sulfur battery and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000005077 polysulfide Substances 0.000 claims abstract description 13
- 229920001021 polysulfide Polymers 0.000 claims abstract description 13
- 150000008117 polysulfides Polymers 0.000 claims abstract description 13
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 claims abstract description 9
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 238000001694 spray drying Methods 0.000 claims abstract description 8
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims abstract description 4
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000903 blocking effect Effects 0.000 claims abstract description 3
- 238000003763 carbonization Methods 0.000 claims abstract description 3
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229940071125 manganese acetate Drugs 0.000 claims abstract description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 11
- 239000006229 carbon black Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 3
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 3
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 3
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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- 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 ternary material functional diaphragm of a lithium-sulfur battery and a preparation method thereof. The ternary material functional diaphragm of the lithium-sulfur battery comprises a diaphragm and a ternary material coating coated on the diaphragm and used for blocking polysulfide shuttling, wherein the ternary material is LiNi0.5Co0.2Mn0.3O2A material. The preparation method of the invention takes nickel acetate, cobalt acetate and manganese acetate as raw materials, and LiNi is synthesized by methods of spray drying, pre-oxidation, carbonization and the like0.5Co0.2Mn0.3O2A material. The ternary material used in the invention has excellent conductivity and adsorptivity and the preparation method is simple, and the functional diaphragm prepared from the ternary material can adsorb polysulfide generated by electrochemical reaction of the lithium-sulfur battery and inhibit shuttle effect. In addition, ternary materials with catalytic activity accelerate the conversion between lithium sulfide and polysulfides, increasing the reaction kinetics inside the cell. Assemble the sameThe lithium-sulfur battery with the functional diaphragm shows good cycle and rate performance.
Description
Technical Field
The invention relates to a functional diaphragm and a preparation method thereof, in particular to a ternary material functional diaphragm of a lithium-sulfur battery and a preparation method thereof, and belongs to the technical field of lithium-sulfur batteries.
Background
In recent years, power generation by new energy sources such as solar energy, wind energy and the like becomes an efficient technical way for relieving energy crisis and environmental pollution. However, the development of new energy generation and smart grid is limited by the technology of high capacity energy storage batteries. At present, lithium ion batteries are one of the key development directions of high-capacity energy storage batteries due to the advantages of good safety, long cycle life, high working voltage and the like.
With the rapid development of electric vehicles, the conventional lithium ion battery cannot meet the requirement of endurance mileage. The lithium-sulfur battery has a plurality of excellent performances such as high energy density, high specific capacity, abundant natural resources and eco-friendliness, and is considered as the most promising next-generation energy storage system. However, there are still many problems that limit the commercial use of lithium sulfur batteries. The shuttling effect and low electrochemical kinetics of polysulfides have always been the most critical challenges.
In the charging and discharging processes of the lithium sulfur battery, long-chain polysulfide can be well dissolved in ether electrolyte, and the dissolved polysulfide freely shuttles between a positive electrode and a negative electrode in the redox process, so that the loss of active substances and specific discharge capacity is caused, and the shuttling effect is realized. Research shows that the introduction of the functional diaphragm can effectively inhibit the shuttle effect. However, most of the current functional membranes can only block shuttling of polysulfides, and are flat for promoting reaction kinetics.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a ternary material functional diaphragm of a lithium-sulfur battery, which can improve the reaction kinetics; the invention also aims to provide a preparation method of the ternary material functional diaphragm of the lithium-sulfur battery.
The technical scheme is as follows: the lithium-sulfur battery ternary material functional diaphragm comprises a diaphragm and a ternary material coating coated on the diaphragm and used for blocking polysulfide shuttling, wherein the ternary material is LiNi0.5Co0.2Mn0.3O2A material.
Further LiNi0.5Co0.2Mn0.3O2The material comprises a plurality of spherical particles, the diameter of which is 5-20 μm.
On the other hand, the preparation method of the ternary material functional diaphragm of the lithium-sulfur battery comprises the following steps:
(1) obtaining LiNi by spray drying0.5Co0.2Mn0.3O2The precursor powder of (4);
(2) pre-oxidizing the precursor powder, grinding and mixing the precursor powder with lithium salt, and carbonizing the mixture to obtain LiNi0.5Co0.2Mn0.3O2A material; wherein the precursor powder is oxidized and calcined under the air condition to achieve the purpose of pre-oxidation.
Further, the spray drying method in the step (1) comprises the following steps of mixing a nickel source, a cobalt source and a manganese source according to a molar ratio of 5: 2: 3, dissolving in 100ml of deionized water, stirring for 30 minutes to form a uniform precursor solution, conveying the precursor solution by a peristaltic pump, and performing ultrasonic atomization drying to obtain precursor powder.
Further, the nickel source is nickel sulfate, nickel acetate or nickel nitrate; the cobalt source is cobalt sulfate, cobalt acetate or cobalt nitrate; the manganese source is manganese sulfate, manganese acetate or manganese nitrate.
Furthermore, the concentration of the precursor solution is 0.25-1 mol/L.
Furthermore, the rotation speed of the peristaltic pump is 2-6rpm, the temperature of the air outlet is 160-200 ℃, and the frequency of the fan is 50-60 Hz.
Further, in the step (2), the lithium salt is lithium carbonate or lithium acetate.
Further, in the step (2), the pre-oxidation temperature is 400-600 ℃, and the time is 1-5 h.
Further, in the step (2), the temperature of the carbonization treatment is 700-900 ℃, and the time is 9-12 h.
On one hand, the spherical ternary material coating can be used as a barrier layer of polysulfide shuttle, and the layered ternary material has strong adsorption effect on long-chain polysulfide due to the existence of a spinel phase, a layered phase and a rock salt phase; on the other hand, nickel, cobalt and manganese in the ternary material are used as transition metals, and the special electronic structure of the ternary material has excellent catalytic activity on polysulfide, so that the oxidation-reduction reaction is effectively promoted, and the electrochemical performance of the lithium-sulfur battery is further improved.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the reaction kinetics in the battery are improved, the spherical ternary material is regular in shape, uniform in particle size and large in specific surface area, and transmission of electrons and ions is facilitated;
(2) improves the cycle and rate performance of the battery and adopts a ternary material LiNi0.5Co0.2Mn0.3O2The crystal has many active reaction sites, the adsorption capacity to long-chain polysulfide is enhanced, the shuttle effect is effectively inhibited, and the utilization rate of active materials is improved;
(3) the preparation method is simple and easy to implement and low in cost, and the controllable synthesis of the ternary material is realized by regulating and controlling the concentration of the precursor solution, the temperature of an air outlet, the rotating speed of a peristaltic pump and the rotating speed of a fan;
(4) the test shows that LiNi is introduced0.5Co0.2Mn0.3O2The battery with the ternary material functional diaphragm has excellent long circulation and rate performance, thereby providing feasibility for the ternary materials with different metal proportions to be used as the functional diaphragm of the lithium-sulfur battery and providing a new idea for solving the technical problem of the lithium-sulfur battery.
Drawings
FIG. 1 is an X-ray diffraction pattern of the ternary functional separator prepared in example 1;
FIG. 2 is a scanning electron microscope image of the ternary functional separator prepared in example 1;
FIG. 3 is a graph of the cycling performance of the ternary material modified lithium sulfur battery prepared in example 1 and a comparative battery at 1C constant current;
fig. 4 is a graph of rate performance of ternary material modified lithium sulfur batteries prepared in example 1 and comparative batteries.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
1. Preparation of ternary material functional diaphragm of lithium-sulfur battery
(1) 6.22g of nickel acetate tetrahydrate, 2.49g of cobalt acetate tetrahydrate, 3.68g of manganese acetate tetrahydrate and 100mL of ionized water are sequentially added into a 250mL beaker, and stirred for 30 minutes by a magnetic stirrer at room temperature to obtain a uniform precursor solution. And transferring the uniform precursor solution to a spray dryer, setting the speed of a peristaltic pump to be 2rpm, the temperature of an air outlet to be 200 ℃ and the frequency of a fan to be 50Hz, and obtaining precursor powder of the ternary material by a spray drying method.
(2) And (3) heating the obtained ternary material precursor powder to 550 ℃ at the heating rate of 5 ℃ per minute in a muffle furnace under the air condition, and preserving the temperature for 5 hours to obtain oxide powder.
(3) Mixing oxide powder with a mass ratio of 1: and (3) fully mixing and grinding the excessive lithium carbonate of 1.05, transferring the mixture into an alumina crucible, placing the alumina crucible into a tubular furnace, heating the mixture to 780 ℃ at the rate of temperature rise of 5 ℃ per minute in pure oxygen atmosphere, preserving the heat for 12 hours, cooling the mixture to room temperature, taking the mixture out, grinding the mixture until no obvious particles exist, and transferring the mixture into a vacuum drying oven.
2. Preparation of lithium-sulfur battery by ternary material functional diaphragm
(1) Weighing 50mg of polyvinylidene fluoride, 400mg of elemental sulfur and 50mg of carbon black, uniformly grinding, dissolving in 400 mu L of N-methyl pyrrolidone, and uniformly stirring to obtain the C/S composite slurry. The slurry was applied to one side of an aluminum foil, vacuum dried for 12 hours, and then cut out into a disk with a diameter of 12mm on a sheet punch as the positive electrode of the cell.
(2) Weighing 40mg of ternary material, 50mg of carbon black and 1g of LA133 with the mass fraction of 1% in 100 mu L of solvent (the volume ratio of water to n-propanol is 1: 3), and uniformly stirring to obtain the composite slurry. The slurry was applied to one side of a blank separator (Celgard 2325), vacuum-dried for 12 hours, and then cut out into a circular sheet having a diameter of 19mm on a punch machine as a separator of a battery.
(3) The cell assembly was carried out in a glove box, the lithium sheet was the negative electrode, the electrolyte was a1, 3 epoxypentane/ethylene glycol dimethyl ether (volume ratio 1:1) solution containing 1M lithium bistrifluoromethylsulfonate (LiTFSI), and 1% of an additive of LiNO3 was added.
3. Preparation of lithium-sulfur battery by carbon black functional diaphragm
The ternary material was replaced with carbon black as a comparative battery, with the other conditions unchanged.
4. Battery performance testing
After the battery is kept still for 10 hours, the constant current density charge-discharge cycle performance test and the multiplying power performance test are completed by a Xinwei test system, and the test voltage interval is 1.7V-2.8V. The current densities for the rate capability test were 0.1C, 0.5C, 1C, 1.5C, 2C, 2.5C (1C 1675 mAh/g).
The X-ray diffraction pattern (FIG. 1) indicates that the method successfully produces LiNi0.5Co0.2Mn0.3O2The ternary material and the ternary material prepared by the method have excellent crystallinity.
A scanning electron microscope image (figure 2) shows that the ternary material prepared by the method is spherical, the diameter is about 20 microns, the particles are uniform, the specific surface area is large, and the rate capability of the battery is improved.
The cycle performance diagram (figure 3) under constant current density shows that under the current density of 1C (1C: 1675mAh/g), the initial capacity of the material for the lithium-sulfur battery is 550mAh/g, the capacity is still 420mAh/g after 300 cycles, the capacity retention rate reaches 80%, the capacity loss rate per cycle is 0.067%, and the coulombic efficiency is close to 100%. While the initial capacity of the pure carbon black material for the lithium-sulfur battery is 350mAh/g, and the capacity is only 190mAh/g after 300 cycles of cycling, and the comparison proves that the ternary material improves the cycling performance of the battery.
The rate performance graph (fig. 4) proves that the specific discharge capacity of the ternary material for the lithium-sulfur battery at different current densities is higher than that of a pure carbon black material for the lithium-sulfur battery, particularly at a current density of 2.5C, the specific capacity of the battery is maintained at 400mAh/g, the capacity can be maintained at 450mAh/g when the current density is recovered to 1.5C, while the specific capacity of the battery is only 300mAh/g when the current density is recovered to 1.5C when the pure carbon black material is recovered to 2.5C, and the capacity is maintained at 350 mAh/g. Therefore, the introduction of the ternary material improves the charge-discharge performance of the lithium-sulfur battery under high current, and the ternary material provides more reaction active sites densely with a layered space structure.
Example 2
The preparation method of the ternary material functional diaphragm of the lithium-sulfur battery comprises the following steps:
(1) 3.11g of nickel acetate tetrahydrate, 1.25g of cobalt acetate tetrahydrate, 1.84g of manganese acetate tetrahydrate and 100mL of ionized water are sequentially added into a 250mL beaker, and stirred for 30 minutes by a magnetic stirrer at room temperature to obtain a uniform precursor solution. And transferring the uniform precursor solution to a spray dryer, setting the speed of a peristaltic pump to be 6rpm, the temperature of an air outlet to be 160 ℃ and the frequency of a fan to be 60Hz, and obtaining precursor powder of the ternary material by a spray drying method.
(2) And (3) heating the obtained ternary material precursor powder to 600 ℃ at the heating rate of 5 ℃ per minute in a muffle furnace under the air condition, and preserving the temperature for 1 hour to obtain oxide powder.
(3) Mixing oxide powder with a mass ratio of 1: and (3) fully mixing and grinding the excessive lithium carbonate of 1.05, transferring the mixture into an alumina crucible, placing the alumina crucible into a tubular furnace, heating the mixture to 700 ℃ at the heating rate of 5 ℃ per minute in the pure oxygen atmosphere, preserving the heat for 9 hours, cooling the mixture to room temperature, taking the mixture out, grinding the mixture until no obvious particles exist, and transferring the mixture into a vacuum drying oven.
The functional separator and the lithium sulfur battery prepared using the ternary material prepared in the above-described method were prepared using the same method as in example and were tested, and the test results showed that the functional separator prepared using the method of example 2 had similar effects to example 1.
Example 3
The preparation method of the ternary material functional diaphragm of the lithium-sulfur battery comprises the following steps:
(1) 12.44g of nickel acetate tetrahydrate, 4.98g of cobalt acetate tetrahydrate, 7.35g of manganese acetate tetrahydrate and 100mL of ionized water are sequentially added into a 250mL beaker, and stirred for 30 minutes by a magnetic stirrer at room temperature to obtain a uniform precursor solution. And transferring the uniform precursor solution to a spray dryer, setting the speed of a peristaltic pump to be 2rpm, the temperature of an air outlet to be 200 ℃ and the frequency of a fan to be 50Hz, and obtaining precursor powder of the ternary material by a spray drying method.
(2) And (3) heating the obtained ternary material precursor powder to 400 ℃ at the heating rate of 5 ℃ per minute in a muffle furnace under the air condition, and preserving the temperature for 4 hours to obtain oxide powder.
(3) Mixing oxide powder with a mass ratio of 1: and (3) fully mixing and grinding the excessive lithium carbonate of 1.05, transferring the mixture into an alumina crucible, placing the alumina crucible into a tubular furnace, heating the mixture to 900 ℃ at the heating rate of 5 ℃ per minute in the pure oxygen atmosphere, preserving the heat for 12 hours, cooling the mixture to room temperature, taking the mixture out, grinding the mixture until no obvious particles exist, and transferring the mixture into a vacuum drying oven.
The functional separator and the lithium sulfur battery prepared using the ternary material prepared in the above-described method were prepared using the same method as in example and were tested, and the test results showed that the functional separator prepared using the method of example 3 had similar effects to example 1.
Claims (10)
1. The ternary material functional diaphragm of the lithium-sulfur battery is characterized by comprising a diaphragm and a ternary material coating coated on the diaphragm and used for blocking polysulfide shuttling, wherein the ternary material is LiNi0.5Co0.2Mn0.3O2A material.
2. The lithium sulfur battery ternary material functional separator according to claim 1, wherein LiNi0.5Co0.2Mn0.3O2The material comprises a plurality of spherical particles, the diameter of which is 5-20 μm.
3. A method for preparing the ternary functional separator for the lithium-sulfur battery according to any one of claims 1 to 2, comprising the following steps:
(1) obtaining LiNi by spray drying0.5Co0.2Mn0.3O2The precursor powder of (4);
(2) pre-oxidizing the precursor powder, grinding and mixing the precursor powder with lithium salt, and carbonizing the mixture to obtain LiNi0.5Co0.2Mn0.3O2A material.
4. The preparation method according to claim 3, wherein the spray drying method in the step (1) is to dissolve the nickel source, the cobalt source and the manganese source in water to form a precursor solution, and then the precursor solution is conveyed by a peristaltic pump and subjected to ultrasonic atomization drying to obtain precursor powder.
5. The method according to claim 4, wherein the nickel source is nickel sulfate, nickel acetate or nickel nitrate; the cobalt source is cobalt sulfate, cobalt acetate or cobalt nitrate; the manganese source is manganese sulfate, manganese acetate or manganese nitrate.
6. The method according to claim 4, wherein the concentration of the precursor solution is 0.25 to 1 mol/L.
7. The method as claimed in claim 4, wherein the speed of the peristaltic pump is 2-6rpm, the outlet temperature is 160-200 ℃, and the frequency of the blower is 50-60 Hz.
8. The production method according to claim 3, wherein in the step (2), the lithium salt is lithium carbonate or lithium acetate.
9. The preparation method as claimed in claim 3, wherein in the step (2), the pre-oxidation temperature is 400-600 ℃ and the time is 1-5 h.
10. The preparation method as claimed in claim 3, wherein the carbonization treatment in step (2) is carried out at a temperature of 700 ℃ and 900 ℃ for a period of 9-12 h.
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| CN110957455A (en) * | 2019-11-27 | 2020-04-03 | 烟台大学 | Functionalized diaphragm for lithium-sulfur battery and preparation method thereof |
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