CN107768630B - A kind of preparation method of metal boride and sulfur composite nanomaterial and its application - Google Patents
A kind of preparation method of metal boride and sulfur composite nanomaterial and its application Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 61
- 239000002184 metal Substances 0.000 title claims abstract description 61
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 46
- 239000011593 sulfur Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 239000000243 solution Substances 0.000 claims abstract description 37
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000005457 ice water Substances 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 37
- 229910052786 argon Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- 239000002077 nanosphere Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims description 2
- -1 nanoarrays Substances 0.000 claims description 2
- 239000002057 nanoflower Substances 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052744 lithium Inorganic materials 0.000 abstract description 12
- 239000005077 polysulfide Substances 0.000 abstract description 10
- 229920001021 polysulfide Polymers 0.000 abstract description 10
- 150000008117 polysulfides Polymers 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 8
- WRSVIZQEENMKOC-UHFFFAOYSA-N [B].[Co].[Co].[Co] Chemical compound [B].[Co].[Co].[Co] WRSVIZQEENMKOC-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- BQBYSLAFGRVJME-UHFFFAOYSA-L molybdenum(2+);dichloride Chemical compound Cl[Mo]Cl BQBYSLAFGRVJME-UHFFFAOYSA-L 0.000 description 4
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- QVCGXRQVUIKNGS-UHFFFAOYSA-L cobalt(2+);dichloride;hydrate Chemical compound O.Cl[Co]Cl QVCGXRQVUIKNGS-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000002033 PVDF binder 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development 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
- 239000011888 foil Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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Abstract
一种金属硼化物和硫复合纳米材料的制备方法及其应用，属于能源材料技术领域。所述方法如下：在惰性气体保护条件下将还原剂和NaOH溶于去离子水中，金属盐溶于去离子水中，将得到的两种溶液分开置于冰水浴中；在惰性气体保护条件下，将步骤一中的金属盐水溶液缓慢加入还原剂溶液中，搅拌30min，之后高温煅烧2~10h，即得到金属硼化物；将金属硼化物与单质硫按照1:1~4的质量比混合，在150~180℃温度下加热煅烧12~24h，得到金属硼化物和硫复合纳米材料。本发明的优点：金属硼化物具有很好的多硫化锂吸附能力，能够提升锂硫电池的稳定性；通过不同的煅烧温度和时间可以控制金属硼化物中结晶度和缺陷位，从而控制锂硫电池整体的性能；成本低，工艺简单，制备过程清洁环保。
The invention relates to a preparation method and application of a metal boride and sulfur composite nanomaterial, belonging to the technical field of energy materials. The method is as follows: under the protection of an inert gas, the reducing agent and NaOH are dissolved in deionized water, the metal salt is dissolved in the deionized water, and the obtained two solutions are separately placed in an ice-water bath; under the protection of an inert gas, The metal salt aqueous solution in step 1 is slowly added to the reducing agent solution, stirred for 30 min, and then calcined at a high temperature for 2-10 h to obtain metal boride; the metal boride and elemental sulfur are mixed in a mass ratio of 1:1 to 4, and the Heating and calcining at 150~180℃ for 12~24h, the metal boride and sulfur composite nanomaterials are obtained. The advantages of the present invention: metal borides have good adsorption capacity of lithium polysulfide, which can improve the stability of lithium-sulfur batteries; crystallinity and defect sites in metal borides can be controlled by different calcination temperatures and times, thereby controlling lithium-sulfur The overall performance of the battery; the cost is low, the process is simple, and the preparation process is clean and environmentally friendly.
Description
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a preparation method and application of a metal boride and sulfur composite nano material.
Background
With the development of the portable electronic industry, the demand for batteries with high specific energy is more urgent, and the lithium ion batteries are limited by the restriction of the specific capacity of the traditional materials such as lithium cobaltate and lithium manganate, and the lithium ion batteries cannot meet the increasing demand. It is imperative to seek a secondary battery with a higher specific capacity. The lithium-sulfur battery is paid attention by researchers in recent years, has the characteristics of high specific capacity (1675 mAh/g), low cost, wide elemental sulfur source, no toxicity and the like, and is expected to become a next-generation commercialized secondary battery system.
However, there are still many difficulties restricting the commercialization of lithium-sulfur batteries, such as: (1) elemental sulfur, a positive electrode material, affects the electrochemical performance of the entire battery due to its inherent insulator properties; (2) the discharge potential of 2.1V is relatively low; (3) lithium polysulfide, an intermediate product of discharge, is easily dissolved in ether electrolyte (shuttle effect), so that sulfur is transferred to the surface of a negative electrode through the electrolyte, and the service life of the battery is shortened; (4) the volume expansion of the elemental sulfur in the discharge process is serious, and potential safety hazards exist. Among the above problems, the dissolution of lithium polysulfide is a major problem to be solved at present.
The shuttle effect is usually solved by compounding the selected material with elemental sulfur and coating the elemental sulfur and the discharge intermediate product in the pore canal of the material. The carbon material belongs to a nonpolar molecule, forms physical adsorption with lithium polysulfide, and has no obvious effect of inhibiting shuttle effect. The polar metal compounds have chemical and physical adsorption and become hot spots for inhibiting the shuttling effect. However, the main focus of the current research is whether to inhibit the shuttling effect, and few people consider the problem of the reaction progress in the discharging process of the lithium-sulfur battery, such as: the conversion process from lithium polysulfide to lithium sulfide is accelerated, and the problem of lithium polysulfide is indirectly inhibited, so that the cycle performance of the lithium-sulfur battery is improved.
Disclosure of Invention
The invention aims to solve the problem of shuttle effect of lithium polysulfide in a lithium-sulfur battery, and provides a preparation method and application of a metal boride and sulfur composite nano material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a metal boride and sulfur composite nanomaterial, the method comprising the steps of:
the method comprises the following steps: dissolving sodium borohydride and NaOH in deionized water under the protection of inert gas to obtain a reducing agent solution, wherein the concentrations of the sodium borohydride and the NaOH are both 0.5-3M; dissolving metal salt in deionized water to obtain 0.5-2M metal salt water solution, and placing the obtained reducing agent solution and metal salt water solution in ice water bath for 15 min;
step two: under the protection of inert gas, slowly adding the metal salt aqueous solution subjected to ice-water bath into the reducing agent solution with the same volume at a speed of one drop per second, stirring for 30min to obtain a dried product, and then calcining the dried product at the temperature of 350-500 ℃ for 2-10 h to obtain metal boride;
step three: mixing metal boride and elemental sulfur according to the mass ratio of 1: 1-4, and heating and calcining at the temperature of 150-180 ℃ for 12-24 hours to obtain the metal boride and sulfur composite nano material.
The application of the metal boride and sulfur composite nano material prepared by the method in the positive electrode of a lithium-sulfur battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) the metal boride has good lithium polysulfide adsorption capacity and can improve the stability of the lithium-sulfur battery.
(2) The metal boride has excellent catalytic activity, can promote the conversion of lithium polysulfide to lithium sulfide, catalyze the discharge process of a lithium-sulfur battery, and reduce the dissolution of the lithium polysulfide.
(3) The crystallinity and defect sites in the metal boride can be controlled through different calcination temperatures and times, thereby controlling the overall performance of the lithium sulfur battery.
(4) Compared with the traditional method for preparing the metal boride at high temperature and high pressure, the method has the advantages of low cost of raw materials, simple preparation process, capability of reacting at room temperature, and clean and environment-friendly preparation process.
Drawings
FIG. 1 is a low-magnification SEM image of molybdenum boride prepared according to the invention;
FIG. 2 is a high magnification SEM image of molybdenum boride prepared in accordance with the present invention;
FIG. 3 is a first charge-discharge curve diagram of the molybdenum boride and sulfur composite nanomaterial prepared by the present invention as a positive electrode of a lithium-sulfur battery;
FIG. 4 is a 0.1C discharge cycle curve diagram of the molybdenum boride and sulfur composite nanomaterial prepared by the present invention as a lithium-sulfur battery anode.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
The first embodiment is as follows: the embodiment describes a method for preparing a metal boride and sulfur composite nano material, which comprises the following steps:
the method comprises the following steps: dissolving sodium borohydride and NaOH in deionized water under the protection of inert gas to obtain a reducing agent solution, wherein the concentrations of the sodium borohydride and the NaOH are both 0.5-3M; dissolving metal salt in deionized water to obtain 0.5-2M metal salt water solution, and placing the obtained reducing agent solution and metal salt water solution in ice water bath for 15 min;
step two: under the protection of inert gas, slowly adding the metal salt aqueous solution subjected to ice-water bath into the reducing agent solution with the same volume at a speed of one drop per second, stirring for 30min to obtain a dried product, and then calcining the dried product at the temperature of 350-500 ℃ for 2-10 h to obtain metal boride;
step three: mixing metal boride and elemental sulfur according to the mass ratio of 1: 1-4, and heating and calcining at the temperature of 150-180 ℃ for 12-24 hours to obtain the metal boride and sulfur composite nano material.
The second embodiment is as follows: in the preparation method of the metal boride and sulfur composite nanomaterial according to the first embodiment, in the first step, the metal salt is one of iron salt, cobalt salt, nickel salt and molybdenum salt.
The third concrete implementation mode: in the second step, the morphology of the metal boride is one of nanowire, nanorod, nanosphere, nanosheet, nanoparticle, nanoarray, nanoflower and nanocube, and is determined by the experimental temperature, the addition speed and the concentration of the metal boride; the surface defects of the material can be regulated and controlled by the calcination temperature.
The fourth concrete implementation mode: in the preparation method of the metal boride and sulfur composite nanomaterial according to the first embodiment, in the first step and the second step, the inert gas is one of argon, nitrogen and a hydrogen-argon mixture.
The fifth concrete implementation mode: one embodiment is a use of the metal boride and sulfur composite nanomaterial prepared by the method of any one of the first to fourth embodiments in a positive electrode of a lithium-sulfur battery.
The sixth specific implementation mode: the application of the metal boride and sulfur composite nanomaterial described in the embodiment five in the positive electrode of a lithium-sulfur battery is as follows: and mixing the metal boride and sulfur composite nano material with a conductive agent and a binder, and drying in an oven at 40-80 ℃ to obtain the lithium-sulfur battery cathode material.
The seventh embodiment: the application of the metal boride and sulfur composite nanomaterial in the positive electrode of the lithium-sulfur battery is characterized in that: the mass fraction of the metal boride and sulfur composite nano material is 50-80%, and the mass ratio of the conductive agent to the binder is 1: 1.
example 1:
(1) dissolving 2.732g of hydrated molybdenum chloride into 20mL of deionized water, stirring for 30min under the protection of argon, and placing in an ice water bath; slowly adding 1mol/L NaBH4Stirring the sodium hydroxide solution for 30min, generating a large amount of bubbles in the adding process and generating black precipitates, filtering the solution after the bubbles disappear, washing with ethanol, and drying to obtain molybdenum boride;
(2) averagely dividing the prepared molybdenum boride into two parts, and calcining the two parts at 350 ℃ and 500 ℃ for 10 hours in argon atmosphere to obtain molybdenum borides with different crystallinities;
(3) and uniformly grinding 50 mg of molybdenum boride and 200 mg of pure sulfur, putting the mixture into a tube furnace, introducing argon as protective gas, and calcining the mixture for 12 hours at 155 ℃ to obtain the molybdenum boride and sulfur composite nano material.
Example 2:
(1) 3.126g of cobalt chloride hydrate is dissolved in 20mL of deionized water, stirred for 30min under the protection of argon and placed in an ice water bath; adding 1mol/L NaBH4Adding the sodium hydroxide solution into the molybdenum chloride solution, continuously stirring for 30min, generating a large amount of bubbles and generating black precipitates in the adding process, and pumping the solution after the bubbles disappearFiltering, washing with ethanol, and drying to obtain cobalt boride;
(2) averagely dividing the prepared molybdenum cobaltate into two parts, and calcining the two parts at 350 ℃ and 500 ℃ for 10 hours in argon atmosphere to obtain cobalt borides with different crystallinities;
(3) and uniformly grinding 50 mg of cobalt boride and 200 mg of pure sulfur, putting the mixture into a tube furnace, introducing argon as protective gas, and calcining the mixture for 12 hours at 155 ℃ to obtain the cobalt boride and sulfur composite nano material.
Example 3:
(1) dissolving 2.732g of hydrated molybdenum chloride into 20mL of deionized water, stirring for 30min under the protection of argon, and placing in an ice water bath; slowly adding 1mol/L NaBH4Stirring the sodium hydroxide solution for 30min, generating a large amount of bubbles in the adding process and generating black precipitates, filtering the solution after the bubbles disappear, washing with ethanol, and drying to obtain molybdenum boride;
(2) evenly dividing the prepared molybdenum boride into three parts, and calcining the three parts at 350 ℃, 500 ℃ and 1000 ℃ for 10 hours in argon atmosphere to obtain molybdenum borides with different crystallinities;
(3) and uniformly grinding 50 mg of molybdenum boride and 200 mg of pure sulfur, putting the mixture into a tube furnace, introducing argon as protective gas, and calcining the mixture for 12 hours at 155 ℃ to obtain the molybdenum boride and sulfur composite nano material.
Example 4:
(1) 3.126g of cobalt chloride hydrate is dissolved in 20mL of deionized water, stirred for 30min under the protection of argon and placed in an ice water bath; adding 1mol/L NaBH4Adding the sodium hydroxide solution into a molybdenum chloride solution, continuously stirring for 30min, generating a large amount of bubbles in the adding process, generating black precipitates, performing suction filtration on the solution after the bubbles disappear, washing with ethanol, and drying to obtain cobalt boride;
(2) evenly dividing the prepared cobalt boride into three parts, and calcining the three parts at 350 ℃, 500 ℃ and 1000 ℃ for 10 hours in argon atmosphere to obtain cobalt borides with different crystallinities;
(3) and uniformly grinding 50 mg of cobalt boride and 200 mg of pure sulfur, putting the mixture into a tube furnace, introducing argon as protective gas, and calcining the mixture for 12 hours at 155 ℃ to obtain the cobalt boride and sulfur composite nano material.
Example 5:
(1) 2.613g of hydrated nickel chloride is taken and dissolved in 20mL of deionized water, stirred for 30min under the protection of argon and placed in an ice water bath; 1mol/L of KBH4Adding the sodium hydroxide solution into a nickel chloride solution, continuously stirring for 30min, generating a large amount of bubbles in the adding process, generating black precipitates, performing suction filtration on the solution after the bubbles disappear, washing with ethanol, and drying to obtain nickel boride;
(2) averagely dividing the prepared nickel boride into two parts, and calcining the two parts at 350 ℃ and 500 ℃ for 10 hours in argon atmosphere to obtain nickel borides with different crystallinities;
(3) and uniformly grinding 50 mg of nickel boride and 200 mg of pure sulfur, putting the mixture into a tube furnace, introducing argon as protective gas, and calcining the mixture for 12 hours at 155 ℃ to obtain the nickel boride and sulfur composite nano material.
Example 6:
(1) dissolving 2.732g of hydrated nickel chloride into 20mL of deionized water, stirring for 30min under the protection of argon, and placing in an ice water bath; 1mol/L of KBH4Adding the sodium hydroxide solution into a nickel chloride solution, continuously stirring for 30min, generating a large amount of bubbles in the adding process, generating black precipitates, performing suction filtration on the solution after the bubbles disappear, washing with ethanol, and drying to obtain nickel boride;
(2) evenly dividing the prepared nickel boride into three parts, and calcining the three parts at 350 ℃, 500 ℃ and 1000 ℃ for 10 hours in argon atmosphere to obtain nickel borides with different crystallinities;
(3) and uniformly grinding 50 mg of nickel boride and 200 mg of pure sulfur, putting the mixture into a tube furnace, introducing argon as protective gas, and calcining the mixture for 12 hours at 155 ℃ to obtain the nickel boride and sulfur composite nano material.
Example 7:
(1) respectively adding 1mol/L NaBH under the protection of argon4Dissolving in 0.1mol/L NaOH, dissolving 0.05 mol/L molybdenum dichloride in 100mL water to obtain 0.5mol/L molybdenum dichloride aqueous solution, and obtaining NaBH4The solution and aqueous molybdenum dichloride solution were placed in an ice water bath.
In the step, the argon protection is to avoid the existence of oxygen in the reaction process to influence the product components.
(2) Slowly adding NaBH into molybdenum dichloride aqueous solution under the protection of inert gas through a syringe4In the solution, black molybdenum boride precipitate is obtained. And calcining the obtained substance at different temperatures under the protection of argon to obtain the molybdenum boride materials with different defect degrees.
(3) Mixing molybdenum boride and elemental sulfur according to the mass ratio of 1:3, and heating and calcining at the temperature of 160 ℃ for 20 hours to obtain the molybdenum boride and sulfur composite nano material.
Example 8:
preparation and performance test of the electrode: mixing a molybdenum boride and sulfur composite nano material, Super P and PVDF according to a mass ratio of 8: 1:1 mixing, using NMP as a solvent to form slurry, stirring for 12 hours, coating the slurry on an aluminum foil to be used as a positive electrode, using metal lithium as a negative electrode, using a Celgard 2400 type diaphragm, dissolving 1mol/L LiTFSI in DOL/DME (volume ratio of 1:1) solvent to be used as an electrolyte, and dissolving 1mol/L LiNO in LiNO3And (4) preparing an additive, and assembling the button cell in a glove box. And (3) carrying out constant-current charge and discharge test by adopting a Newware pool test system, wherein the charge and discharge voltage range is 1.7-2.8V.
Fig. 1 and 2 are SEM pictures of different magnifications of the molybdenum boride and sulfur composite nanomaterial, and it can be seen in the pictures that the molybdenum boride nanospheres are uniform in size and can load a large amount of elemental sulfur.
FIG. 3 shows the charging and discharging curve of the assembled button cell at a current density of 0.2C, the first discharge capacity of 1040mAh g-1。
Fig. 4 is a plot of the assembled button cell at a current density of 0.2C for 100 cycles of charge and discharge, with a capacity retention of 72.73% for 50 cycles and 63.64% for 100 cycles.
Claims (7)
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