CN109950519B - Positive electrode material of lithium-sulfur primary battery and preparation method of positive electrode material - Google Patents
Positive electrode material of lithium-sulfur primary battery and preparation method of positive electrode material Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims abstract description 28
- 239000002086 nanomaterial Substances 0.000 claims abstract description 26
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 22
- 239000010935 stainless steel Substances 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002070 nanowire Substances 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000004570 mortar (masonry) Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000013543 active substance Substances 0.000 description 5
- 229920001021 polysulfide Polymers 0.000 description 5
- 239000005077 polysulfide Substances 0.000 description 5
- 150000008117 polysulfides Polymers 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000012938 design process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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 belongs to the technical field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur primary battery positive electrode material and a preparation method thereof. The anode material is alpha-Fe2O3／SnO2And (3) forming a composite material of the nano material and S. The positive electrode material is applied to the lithium-sulfur primary battery, so that the lithium-sulfur primary battery has high discharge capacity and excellent cycle stability; preparation of alpha-Fe of composite heterostructure by combination of chemical vapor deposition and hydrothermal method2O3/SnO2the/S composite material has the characteristics of high yield, industrial feasibility and the like, and is easy to realize low-cost preparation and large-scale industrialization.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a lithium-sulfur primary battery positive electrode material and a preparation method thereof.
Background
Today, as the human society advances into information, mobile phones, notebook computers, and personal portable terminals are becoming more popular, and are rapidly becoming lighter and smaller, which has made higher demands on the energy density of batteries. In addition, along with the mass emergence of other industrial, civil, medical and military electronic products, especially the development of space technology and novel national defense equipment such as novel satellites, spacecraft, high-power laser weapons, digital soldier systems and the like, the demand for primary batteries with light weight, small volume, high specific energy, high specific power, safety, reliability and no pollution is more urgent. Therefore, the research and development of the primary battery system with high specific energy have very important significance.
Lithium-sulfur batteries have attracted considerable attention worldwide due to their extremely low cost, extremely high specific energy and environmental friendliness, and are one of the most promising power batteries, and their battery systems have very high initial specific discharge capacity, even reaching theoretical values, which makes them suitable for the application of high specific energy primary batteries, and once assembled, they are in a full-charge state, and can directly supply power to a load, and the production and use processes all meet the requirements of primary batteries.
One of the major problems of the current lithium-sulfur primary battery is that the "self-discharge" rate is high, and if the battery is left at room temperature in a full-charge state, the open-circuit voltage of the battery is slowly reduced from 2.3V to 2.15V within one month, and the capacity loss is as high as more than 30%. This is because the electrolyte for lithium-sulfur batteries generally uses 1, 3-dioxolane and ethylene glycol dimethyl ether as solvents and a lithium bistrifluoromethylsulfonyl imide solution as a supporting electrolyte. The electrolyte has certain solubility to elemental sulfur and polysulfide, although the characteristic is favorable for the electrochemical reaction of a sulfur positive electrode, in the long-term shelf process of a lithium sulfur battery, the elemental sulfur slightly soluble in the electrolyte can penetrate through a diaphragm to reach the negative electrode side, a layer of solid electrolyte interface film taking lithium sulfide as a main component is formed on the surface of metal lithium, the lithium sulfide in the layer of interface film can react with the elemental sulfur to generate lithium polysulfide which can be dissolved in the electrolyte, so that the fresh lithium surface is exposed to continue to react with the elemental sulfur or polysulfide in the solution, and meanwhile, the elemental sulfur on the positive electrode side is continuously dissolved out, so that the capacity of the battery is continuously lost, and the open-circuit voltage is rapidly reduced. The problems of small active substance loading capacity and low utilization rate of sulfur active substances appear in the conventional lithium-sulfur primary battery cathode material.
Disclosure of Invention
The invention aims to provide a lithium-sulfur primary battery positive electrode material and a preparation method thereof aiming at the defects, and the positive electrode material is applied to the lithium-sulfur primary battery, so that the lithium-sulfur primary battery has high discharge capacity and excellent cycling stability; preparation of alpha-Fe of composite heterostructure by combination of chemical vapor deposition and hydrothermal method2O3/SnO2the/S composite material has the characteristics of high yield, industrial feasibility and the like, and is easy to realize low-cost preparation and large-scale industrialization.
The technical scheme of the invention is as follows: the positive electrode material of the lithium-sulfur primary battery is alpha-Fe2O3／SnO2Nanomaterial formation with S
The composite material of (1).
The alpha-Fe2O3／SnO2The nano material is a composite heterostructure.
alpha-Fe in mass ratio2O3／SnO2Nano materials: s is 1: 2 to 4.
The composite material is prepared by a method combining a chemical vapor deposition method and a hydrothermal method.
The preparation method of the positive electrode material of the lithium-sulfur primary battery comprises the following steps:
（1）SnO2preparing the nano wire: SnO is added according to the mass ratio of 1:12Grinding and mixing the powder and graphite powder, transferring the mixture into a porcelain boat, and then placing the stainless steel substrate and the porcelain boat into a quartz tube; the furnace temperature is increased to 1050 ℃ at the speed of 50 ℃/min, and the mixture is heated for 1h at 1050 ℃ under the constant conditions of 50sccm argon flow and 15mbar pressure; after cooling to room temperature, SnO2The nanowires were deposited on a stainless steel substrate to obtain deposited SnO2A nanowire;
（2）α-Fe2O3／SnO2preparing a nano material: prepared from SnO2The nanowire-covered stainless steel substrate was placed in a 50mL reaction vessel, and then 30mL of 0.15moL of FeCl was poured into the reaction vessel3And 1moL NaNO3Adjusting the pH value of the aqueous solution to 1.5-3 by using hydrochloric acid with the mass fraction of 36.5%, heating a reaction kettle to 100 ℃, preserving heat for 12-24 hours, cooling to room temperature, removing a stainless steel substrate from the aqueous solution, washing with deionized water, and using N2Drying, and carrying out heat treatment on the obtained product at 450-600 ℃ for 2h in the air atmosphere to obtain the alpha-Fe of the composite heterostructure2O3／SnO2A nanomaterial;
（3）α-Fe2O3／SnO2preparation of the/S composite material: weighing the required alpha-Fe according to the proportion2O3／SnO2Mixing the nano material and S to obtain a mixture, wherein the mass ratio of the nano material to the S is alpha-Fe2O3／SnO2Nano materials: s is 1: 2-4, placing the mixture in a mortar, grinding the mixture into powder, and dripping 10-20 ml of CS into the powder in the mortar2Then sufficiently grinding again, and collecting the ground powderPutting the mixture into a reaction kettle, and carrying out hydrothermal reaction at the heating temperature of 155 ℃ for 12h to obtain alpha-Fe2O3／SnO2a/S composite material.
The stainless steel substrate in the step (1) is coated by Au sputtering to prepare a template so that SnO can be enabled2The powder forms nanowires thereon.
In the step (1), the center of the porcelain boat is positioned at the center of the quartz tube, and the stainless steel substrate is arranged at the downstream of the argon flow. SnO is added during argon introduction2And (5) drying.
The invention has the beneficial effects that: compared with the prior art, the invention has the following prominent substantive characteristics:
(1) in the design process, aiming at solving the problems of small active substance load and low sulfur active substance utilization rate in the anode material of the conventional lithium-sulfur primary battery, the invention innovatively provides a method for preparing alpha-Fe with a composite heterostructure by combining a chemical vapor deposition method and a hydrothermal method2O3/SnO2a/S composite material. The adopted chemical vapor deposition method and hydrothermal method are the simplest and most convenient synthesis means with high yield, and the strategy is easy and effective and is easy to realize alpha-Fe2O3/SnO2Low cost and large-scale industrialization of the preparation of the/S composite material. By Fe2O3And SnO2In the synergistic effect of, in alpha-Fe2O3And SnO2The Fe nano-particles exist at the interface between the two can improve the reversibility of the reaction, and the metal nano-particles formed in situ can electrochemically drive Li2Reversible formation and decomposition of the O nanomatrix and further results in higher reversible capacity.
(2) In the design process of the present invention, alpha-Fe2O3/SnO2The composite heterostructure of the/S composite material can provide a large number of electron and ion transmission channels, promotes the transmission of ions and electrons, and can adapt to the volume expansion in the charging and discharging processes and the exposed SnO2In contrast, pure SnO2The nanowires are easily destroyed by adding the high capacity component alpha-Fe2O3With SnO2The synergistic effect is generated, a better effect can be obtained, the stability of the structure is enhanced, the structure has a large specific surface area, polysulfide can be effectively captured, shuttling of polysulfide is inhibited, the utilization rate of active substances is improved, and further the overall performance of the lithium-sulfur primary battery is improved.
(3) alpha-Fe according to the invention2O3／SnO2The first charge-discharge specific capacity of the lithium-sulfur primary battery composed of the/S composite material reaches 765mAh/g at 0.2 ℃, and the lithium-sulfur primary battery has high discharge capacity and excellent cycling stability.
(4) The method has the characteristics of high yield and industrial feasibility.
Drawings
FIG. 1 shows α -Fe obtained in example 12O3／SnO2the/S composite material is used as a positive electrode material to be applied to an electrochemical charge-discharge curve of a lithium-sulfur primary battery.
FIG. 2 is a view of alpha-Fe2O3／SnO2Scanning images of the/S composite material.
Detailed Description
The invention is further illustrated with reference to the following figures and examples. The raw materials are all obtained by commercial purchase, wherein SnO2 is purchased from Beijing Shengbo Gaotai optical technology Co., Ltd, NaNO3 is purchased from Aladdin Biochemical technology Co., Ltd (Shanghai, China), and the NaNO sulfur powder is purchased from NaNO3 Aladdin Biochemical technology Co., Ltd (Shanghai, China).
Example 1
The positive electrode material of the lithium-sulfur primary battery is alpha-Fe2O3／SnO2And (3) forming a composite material of the nano material and S. The above-mentioned
α-Fe2O3／SnO2The nano material is a composite heterostructure.
alpha-Fe in mass ratio2O3／SnO2Nano materials: s is 1: 3.
the composite material is prepared by a method combining a chemical vapor deposition method and a hydrothermal method.
The preparation method of the positive electrode material of the lithium-sulfur primary battery comprises the following steps:
（1）SnO2preparing the nano wire: SnO is added according to the mass ratio of 1:12Grinding and mixing the powder and graphite powder, transferring the mixture into a porcelain boat, and then placing a stainless steel substrate and the porcelain boat which are coated by Au sputtering into a quartz tube, wherein the center of the porcelain boat is positioned at the center of the quartz tube, and the stainless steel substrate is positioned at the downstream of argon flow; the furnace temperature is increased to 1050 ℃ at the speed of 50 ℃/min, and the mixture is heated for 1h at 1050 ℃ under the constant conditions of 50sccm argon flow and 15mbar pressure; after cooling to room temperature, SnO2The nanowires were deposited on a stainless steel substrate to obtain deposited SnO2A nanowire;
（2）α-Fe2O3／SnO2preparing a nano material: prepared from SnO2The nanowire-covered stainless steel substrate was placed in a 50mL reaction vessel, and then 30mL of 0.15moL of FeCl was poured into the reaction vessel3And 1moL NaNO3Adjusting pH to 1.5 with hydrochloric acid with mass fraction of 36.5%, heating the reaction kettle to 100 deg.C, maintaining the temperature for 12h, cooling to room temperature, removing stainless steel substrate from the solution, repeatedly washing with deionized water, and washing with N2Blow-drying, and then carrying out heat treatment on the obtained product at 450 ℃ in the air atmosphere for 2h to obtain the alpha-Fe of the composite heterostructure2O3／SnO2A nanomaterial;
（3）α-Fe2O3／SnO2preparation of the/S composite material: weighing the required alpha-Fe according to the proportion2O3／SnO2Mixing the nano material and S to obtain a mixture, wherein the mass ratio of the nano material to the S is alpha-Fe2O3／SnO2Nano materials: s is 1: 4, placing the mixture in a mortar, grinding the mixture into uniform fine powder, and dropwise adding 15 ml of CS into the powder in the mortar2Then fully grinding again, collecting the ground powder, putting the powder into a reaction kettle, and carrying out hydrothermal reaction at the heating temperature of 155 ℃ for 12h to obtain the alpha-Fe2O3／SnO2S composite materialAnd (5) feeding.
As can be seen from FIG. 1, α -Fe obtained in this example 1 was observed at a current density of 0.2C2O3／SnO2The first discharge capacity of the/S composite material applied to the lithium-sulfur primary battery as the positive electrode material is up to 765 mAh/g.
As can be seen from FIG. 2, alpha-Fe was synthesized2O3／SnO2the/S composite material presents a dendritic composite heterostructure.
Example 2
The preparation method of the positive electrode material of the lithium-sulfur primary battery comprises the following steps:
（1）SnO2preparing the nano wire: SnO is added according to the mass ratio of 1:12Grinding and mixing the powder and graphite powder, transferring the mixture into a porcelain boat, and then placing a stainless steel substrate and the porcelain boat which are coated by Au sputtering into a quartz tube, wherein the center of the porcelain boat is positioned at the center of the quartz tube, and the stainless steel substrate is positioned at the downstream of argon flow; the furnace temperature is increased to 1050 ℃ at the speed of 50 ℃/min, and the mixture is heated for 1h at 1050 ℃ under the constant conditions of 50sccm argon flow and 15mbar pressure; after cooling to room temperature, SnO2The nanowires were deposited on a stainless steel substrate to obtain deposited SnO2A nanowire;
（2）α-Fe2O3／SnO2preparing a nano material: prepared from SnO2The nanowire-covered stainless steel substrate was placed in a 50mL reaction vessel, and then 30mL of 0.15moL of FeCl was poured into the reaction vessel3And 1moL NaNO3Adjusting pH to 3 with hydrochloric acid with mass fraction of 36.5%, heating the reaction kettle to 100 deg.C, maintaining the temperature for 24 hr, cooling to room temperature, removing stainless steel substrate from the solution, repeatedly washing with deionized water, and washing with N2Blow-drying, and then carrying out heat treatment on the obtained product at 600 ℃ in the air atmosphere for 2h to obtain the alpha-Fe of the composite heterostructure2O3／SnO2A nanomaterial;
（3）α-Fe2O3／SnO2preparation of the/S composite material: weighing the required alpha-Fe according to the proportion2O3／SnO2Nano materialMixing the material and S to obtain a mixture, wherein the mass ratio of alpha-Fe2O3／SnO2Nano materials: s is 1: 4, placing the mixture in a mortar, grinding the mixture into uniform fine powder, and dropwise adding 10 ml of CS into the powder in the mortar2Then fully grinding again, collecting the ground powder, putting the powder into a reaction kettle, and carrying out hydrothermal reaction at the heating temperature of 155 ℃ for 12h to obtain the alpha-Fe2O3／SnO2a/S composite material.
Claims (4)
1. The positive electrode material of the lithium-sulfur primary battery is characterized by being alpha-Fe2O3/SnO2A composite of the nanomaterial and S; the composite material is prepared by the following steps: (1) SnO2Preparing the nano wire: SnO is added according to the mass ratio of 1:12Grinding and mixing the powder and graphite powder, transferring the mixture into a porcelain boat, and then placing the stainless steel substrate and the porcelain boat into a quartz tube; the furnace temperature is increased to 1050 ℃ at the speed of 50 ℃/min, and the mixture is heated for 1h at 1050 ℃ under the constant conditions of 50sccm argon flow and 15mbar pressure; after cooling to room temperature, SnO2The nanowires were deposited on a stainless steel substrate to obtain deposited SnO2A nanowire;
(2)α-Fe2O3/SnO2preparing a nano material: prepared from SnO2The nanowire-covered stainless steel substrate was placed in a 50mL reaction vessel, and then 30mL of 0.15moL of FeCl was poured into the reaction vessel3And 1moL NaNO3Adjusting the pH value of the formed aqueous solution to 1.5-3 by using hydrochloric acid with the mass fraction of 36.5%, heating a reaction kettle to 100 ℃, preserving heat for 12-24 hours, cooling to room temperature, removing a stainless steel substrate from the solution, washing with deionized water, drying with N2, and performing heat treatment on the obtained product at 450-600 ℃ for 2 hours in an air atmosphere to obtain alpha-Fe of a composite heterostructure2O3/SnO2A nanomaterial;
(3)α-Fe2O3/SnO2preparation of the/S composite material: weighing the required alpha-Fe according to the proportion2O3/SnO2Mixing the nano material and S to obtain a mixture, wherein the mass ratio of the nano material to the S is alpha-Fe2O3/SnO2Nano materials: s is 1: 2-4, placing the mixture in a mortar, grinding the mixture into powder, and dripping 10-20 ml of CS into the powder in the mortar2Then fully grinding again, collecting the ground powder, putting the powder into a reaction kettle, and carrying out hydrothermal reaction at the heating temperature of 155 ℃ for 12h to obtain the alpha-Fe2O3/SnO2(ii) a/S composite; synthesized alpha-Fe2O3/SnO2the/S composite material presents a dendritic composite heterostructure.
2. The positive electrode material for a lithium-sulfur primary battery according to claim 1, wherein the composite material is prepared by a combination of a chemical vapor deposition method and a hydrothermal method.
3. The positive electrode material for a lithium-sulfur primary battery according to claim 1, wherein the stainless steel substrate in step (1) is coated by Au sputtering.
4. The positive electrode material for a lithium-sulfur primary battery according to claim 1, wherein the center of the porcelain boat is located at the center of the quartz tube in step (1), and the stainless steel substrate is placed downstream of the argon gas flow.
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| CN107706353A (en) * | 2017-11-21 | 2018-02-16 | 安徽师范大学 | Preparation method, lithium-sulphur cell positive electrode and the battery of the nano composite material of tin ash/manganese dioxide load sulfur granules |
| CN108767243A (en) * | 2018-06-26 | 2018-11-06 | 湖北工程学院 | Fe2O3/SnO2Composite material, preparation method, application and lithium ion battery |
| CN108899500A (en) * | 2018-06-28 | 2018-11-27 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN108878847A (en) * | 2018-07-03 | 2018-11-23 | 西南交通大学 | Lithium sulfur battery anode material and preparation method thereof |
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