CN113314715B - A kind of nickel sulfide composite material and its preparation method and application - Google Patents
A kind of nickel sulfide composite material and its preparation method and application Download PDFInfo
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- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011258 core-shell material Substances 0.000 claims abstract description 13
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 238000004729 solvothermal method Methods 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 10
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 9
- 229940078494 nickel acetate Drugs 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 4
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 230000007774 longterm Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 239000004005 microsphere Substances 0.000 description 17
- -1 Transition metal sulfides Chemical class 0.000 description 11
- 229910052723 transition metal Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910018661 Ni(OH) Inorganic materials 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 4
- 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 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- CLTMFUNLGRYXGD-UHFFFAOYSA-M OC[Ni]O Chemical compound OC[Ni]O CLTMFUNLGRYXGD-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
本发明属于能源存储技术领域，公开了一种硫化镍复合材料及其制备方法和应用。该硫化镍复合材料具有核壳结构，包括内核和外壳，内核包括硫化镍，外壳包括氮掺杂的碳壳。其形貌均一可控，结构稳定，不易出现破碎；氮掺杂的碳壳具有更好的电导性，而碳包覆形成的外壳能够减缓硫化镍内核在长期的充放电过程中引起的体积膨胀，保证材料结构的稳定性；将其作为钠离子电池负极材料，能够提高电池容量和电池的循环稳定性。本发明提供的制备方法，采用三步法即可，制备方法简单，能够得到形貌均一可控的硫化镍复合材料。本发明提供的硫化镍复合材料能够应用于电池的制备中。
The invention belongs to the technical field of energy storage, and discloses a nickel sulfide composite material and a preparation method and application thereof. The nickel sulfide composite material has a core-shell structure, including an inner core and an outer shell, the inner core includes nickel sulfide, and the outer shell includes a nitrogen-doped carbon shell. Its morphology is uniform and controllable, its structure is stable, and it is not easy to be broken; the nitrogen-doped carbon shell has better electrical conductivity, and the shell formed by carbon coating can slow down the volume expansion of the nickel sulfide core during long-term charging and discharging. , to ensure the stability of the material structure; using it as a negative electrode material for sodium-ion batteries can improve battery capacity and battery cycle stability. The preparation method provided by the invention can adopt a three-step method, the preparation method is simple, and a nickel sulfide composite material with uniform and controllable morphology can be obtained. The nickel sulfide composite material provided by the invention can be used in the preparation of batteries.
Description
技术领域technical field
本发明属于能源存储技术领域，具体涉及一种硫化镍复合材料及其制备方法和应用。The invention belongs to the technical field of energy storage, and in particular relates to a nickel sulfide composite material and a preparation method and application thereof.
背景技术Background technique
近年来，由于能源消耗日趋严重，目前最为流行的锂离子电池由于金属锂的大量消耗，研究人员不得不寻找下一代碱金属离子电池。其中，钠离子电池被认为一种有发展前景的可扩展的能量存储和转换***，因其成本低、钠资源丰富，受到广泛关注。In recent years, due to the increasingly serious energy consumption, the most popular lithium-ion battery is currently the most popular lithium-ion battery due to the large consumption of metal lithium, researchers have to look for the next generation of alkali metal-ion batteries. Among them, sodium-ion batteries are considered as a promising scalable energy storage and conversion system, which has attracted extensive attention due to its low cost and abundant sodium resources.
为了获得令人满意的钠离子电池性能，负极材料被认为是最重要的一环。与金属锂相比，金属钠具有更大的原子半径，因此，应用于锂离子电池的传统负极材料(如碳基质材料、过渡金属氧化物等)并不能在钠离子电池中获得较高的容量。寻找新一代的钠离子电池负极材料成为了研究热点。In order to obtain satisfactory Na-ion battery performance, the anode material is considered to be the most important part. Compared with metal lithium, metal sodium has a larger atomic radius, so traditional anode materials (such as carbon matrix materials, transition metal oxides, etc.) applied in lithium-ion batteries cannot achieve high capacity in sodium-ion batteries. . The search for a new generation of anode materials for Na-ion batteries has become a research hotspot.
过渡金属硫化物(TMSs)由于具有较高的理论容量，被认为是潜在的钠离子存储候选材料。但是，过渡金属硫化物的应用也屡屡受挫，主要是由于以下两个方面：(1)与过渡金属氧化物相比，过渡金属硫化物尽管具有较好的电导性，但是这仍然不能满足其应用于钠离子电池；(2)由于过渡金属硫化物在钠离子电池中是以“转化机制”的方式充放电，因此会导致材料膨胀粉碎，在长期循环中无法表现出良好的稳定性能和高容量。Transition metal sulfides (TMSs) have been considered as potential Na-ion storage candidates due to their high theoretical capacities. However, the application of transition metal sulfides has also been repeatedly frustrated, mainly due to the following two aspects: (1) Compared with transition metal oxides, although transition metal sulfides have better electrical conductivity, this still cannot meet its application. (2) Since transition metal sulfides are charged and discharged in a "transformation mechanism" in sodium-ion batteries, they will cause the material to expand and pulverize, and cannot show good stability and high capacity in long-term cycles. .
因此，亟需提供一种硫化镍材料，其结构稳定，作为钠离子电池负极，容量高，循环稳定性强。Therefore, there is an urgent need to provide a nickel sulfide material with stable structure, high capacity and strong cycle stability as a negative electrode for sodium ion batteries.
发明内容SUMMARY OF THE INVENTION
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种硫化镍复合材料，其结构稳定，不易破碎，作为钠离子电池负极材料，容量高，循环稳定性强。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a nickel sulfide composite material, which has a stable structure and is not easily broken. As a negative electrode material for sodium ion batteries, it has high capacity and strong cycle stability.
本发明第一方面提供了一种硫化镍复合材料。A first aspect of the present invention provides a nickel sulfide composite material.
具体的，所述硫化镍复合材料具有核壳结构，包括内核和外壳，所述内核包括硫化镍，所述外壳包括氮掺杂的碳壳。Specifically, the nickel sulfide composite material has a core-shell structure, including an inner core and an outer shell, the inner core includes nickel sulfide, and the outer shell includes a nitrogen-doped carbon shell.
优选的，所述内核的直径为1-1.5μm，所述外壳的厚度为100-150nm。Preferably, the diameter of the inner core is 1-1.5 μm, and the thickness of the outer shell is 100-150 nm.
本发明第二方面提供了一种硫化镍复合材料的制备方法。A second aspect of the present invention provides a method for preparing a nickel sulfide composite material.
具体的，一种硫化镍复合材料的制备方法，包括以下步骤：Specifically, a preparation method of a nickel sulfide composite material, comprising the following steps:
(1)将乙酸镍、表面活性剂溶于醇中，进行溶剂热反应，得到前驱体；(1) dissolving nickel acetate and surfactant in alcohol, and carrying out solvothermal reaction to obtain precursor;
(2)将步骤(1)制得的所述前驱体分散在三(羟甲基)氨基甲烷溶液中，加入盐酸多巴胺，反应，过滤得沉淀，制得包覆体；(2) dispersing the precursor obtained in step (1) in a tris(hydroxymethyl)aminomethane solution, adding dopamine hydrochloride, reacting, filtering to obtain a precipitate, and obtaining a coating;
(3)将步骤(2)制得的所述包覆体与硫混合，煅烧，制得所述硫化镍复合材料。(3) Mixing the coating obtained in step (2) with sulfur, and calcining to obtain the nickel sulfide composite material.
本发明通过溶剂热、原位聚合、煅烧制得所述硫化镍复合材料。首先，乙酸镍与醇(甲醇)进行酯交换反应，同时，以表面活性剂作为软模板，使超薄二维纳米片组装成独特、均一的球状的前驱体(如羟甲基氢氧化镍)；再利用盐酸多巴胺进行表面原位聚合，形成包覆体；最后在碳化/硫化(煅烧)过程中生成了核壳结构的硫化镍复合材料，实现氮掺杂和碳包覆，氮掺杂碳壳极大提升了材料的电化学性能，一方面，相比于纯的碳壳，氮元素掺杂的碳壳具有更好的电导性；另一方面，核壳结构中，碳壳可以减缓硫化镍内核在长期的充放电过程中引起的体积膨胀，从而保证材料结构稳定以及提高其循环寿命。In the present invention, the nickel sulfide composite material is prepared by solvothermal, in-situ polymerization and calcination. First, nickel acetate is transesterified with alcohol (methanol), and at the same time, the ultrathin 2D nanosheets are assembled into unique and uniform spherical precursors (such as hydroxymethyl nickel hydroxide) using surfactants as soft templates. ; Then use dopamine hydrochloride for in-situ polymerization on the surface to form a coating body; finally, a core-shell structure nickel sulfide composite material is generated during the carbonization/sulfidation (calcination) process to realize nitrogen doping and carbon coating, nitrogen doping carbon The shell greatly improves the electrochemical performance of the material. On the one hand, the nitrogen-doped carbon shell has better electrical conductivity than the pure carbon shell; on the other hand, in the core-shell structure, the carbon shell can slow down the vulcanization. The volume expansion of the nickel core during the long-term charge and discharge process ensures the stability of the material structure and improves its cycle life.
所述制备方法中，采用盐酸多巴胺进行原位聚合包覆前驱体，使前驱体表面形成厚度均匀的包覆层，经煅烧处理后，碳包覆层均匀，稳定，不易破碎。发明人研究发现，若采用其他含氮有机物替换盐酸多巴胺，将无法实现均匀包覆，最终形成的碳包覆层不均匀，且易出现核壳破碎的现象。In the preparation method, dopamine hydrochloride is used to polymerize and coat the precursor in situ, so that a coating layer with uniform thickness is formed on the surface of the precursor. After calcination, the carbon coating layer is uniform, stable, and not easily broken. The inventor's research found that if other nitrogen-containing organic substances are used to replace dopamine hydrochloride, uniform coating will not be achieved, and the resulting carbon coating layer will be uneven, and the phenomenon of core-shell fragmentation is prone to occur.
优选的，在步骤(1)中，所述乙酸镍浓度为0.02-0.2mol L-1。Preferably, in step (1), the nickel acetate concentration is 0.02-0.2 mol L- 1 .
优选的，在步骤(1)中，所述表面活性剂为十六烷基三甲基溴化铵或聚乙烯吡咯烷酮。十六烷基三甲基溴化铵或聚乙烯吡咯烷酮在溶剂热反应中有利于诱导超薄纳米片组装成花球，形成前驱体。Preferably, in step (1), the surfactant is cetyltrimethylammonium bromide or polyvinylpyrrolidone. Cetyltrimethylammonium bromide or polyvinylpyrrolidone in a solvothermal reaction is beneficial to induce the assembly of ultrathin nanosheets into curds, forming precursors.
优选的，在步骤(1)中，所述醇为甲醇。Preferably, in step (1), the alcohol is methanol.
优选的，在步骤(1)中，所述表面活性剂的物质的量为所述乙酸镍的物质的量的0.5％-8％；进一步优选的，在步骤(1)中，所述表面活性剂的物质的量为所述乙酸镍的物质的量的1％-5％。Preferably, in step (1), the amount of the surfactant is 0.5%-8% of the amount of the nickel acetate; further preferably, in step (1), the surface active The substance amount of the agent is 1%-5% of the substance amount of the nickel acetate.
优选的，在步骤(1)中，所述溶剂热反应的温度为100-200℃，所述溶剂热反应的时间为12-60h；进一步优选的，在步骤(1)中，所述溶剂热反应的温度为120-200℃，所述溶剂热反应的时间为12-48h。Preferably, in step (1), the temperature of the solvothermal reaction is 100-200°C, and the time of the solvothermal reaction is 12-60 h; further preferably, in step (1), the solvothermal reaction The reaction temperature is 120-200°C, and the solvothermal reaction time is 12-48h.
优选的，在步骤(2)中，所述前驱体采用三(羟甲基)氨基甲烷溶液(Tris溶液)分散，所述三(羟甲基)氨基甲烷溶液的浓度为0.005-0.020mol L-1。三(羟甲基)氨基甲烷溶液不仅能够分散前驱体，还能够起到调节分散液的pH的作用，有利于后续盐酸多巴胺的包覆作用。Preferably, in step (2), the precursor is dispersed with a tris(hydroxymethyl)aminomethane solution (Tris solution), and the concentration of the tris(hydroxymethyl)aminomethane solution is 0.005-0.020mol L- 1 . The tris(hydroxymethyl)aminomethane solution can not only disperse the precursor, but also can adjust the pH of the dispersion, which is beneficial to the subsequent coating of dopamine hydrochloride.
优选的，在步骤(2)中，所述反应的温度为室温(如10-35℃)，所述反应的时间为8-36h。Preferably, in step (2), the reaction temperature is room temperature (eg, 10-35° C.), and the reaction time is 8-36 h.
优选的，在步骤(3)中，所述包覆体与所述硫的质量比例为(1-3)：(1-3)；进一步优选的，在步骤(3)中，所述包覆体与所述硫的质量比例为(1-2)：(1-2)。Preferably, in step (3), the mass ratio of the coating body to the sulfur is (1-3): (1-3); further preferably, in step (3), the coating The mass ratio of the body to the sulfur is (1-2): (1-2).
优选的，在步骤(3)中，所述煅烧过程在氮气气氛中进行。Preferably, in step (3), the calcination process is carried out in a nitrogen atmosphere.
优选的，在步骤(3)中，所述煅烧的温度为300-600℃，煅烧的时间为1-6h；进一步优选的，在步骤(3)中，所述煅烧的温度为300-500℃，煅烧的时间为1-4h。Preferably, in step (3), the calcination temperature is 300-600°C, and the calcination time is 1-6h; further preferably, in step (3), the calcination temperature is 300-500°C , the calcination time is 1-4h.
本发明第三方面提供了所述硫化镍复合材料的应用。The third aspect of the present invention provides the application of the nickel sulfide composite material.
所述硫化镍复合材料在制备电池中的应用。The application of the nickel sulfide composite material in the preparation of batteries.
一种电池负极材料，包括所述硫化镍复合材料。A battery negative electrode material, comprising the nickel sulfide composite material.
一种钠离子电池负极材料，包括所述硫化镍复合材料。A negative electrode material for a sodium ion battery, comprising the nickel sulfide composite material.
一种电池，包括所述硫化镍复合材料。A battery includes the nickel sulfide composite material.
相对于现有技术，本发明的有益效果如下：With respect to the prior art, the beneficial effects of the present invention are as follows:
(1)本发明提供的硫化镍复合材料为具有核壳结构，包括内核和外壳，所述内核包括硫化镍，所述外壳包括氮掺杂的碳壳。其形貌均一可控，结构稳定，不易出现破碎；氮掺杂的碳壳具有更好的电导性，而碳包覆形成的外壳能够减缓硫化镍内核在长期的充放电过程中引起的体积膨胀，保证材料结构的稳定性；将其作为钠离子电池负极材料，能够提高电池容量和电池的循环稳定性。(1) The nickel sulfide composite material provided by the present invention has a core-shell structure, including an inner core and an outer shell, the inner core includes nickel sulfide, and the outer shell includes a nitrogen-doped carbon shell. Its morphology is uniform and controllable, its structure is stable, and it is not easy to be broken; the nitrogen-doped carbon shell has better electrical conductivity, and the shell formed by carbon coating can slow down the volume expansion of the nickel sulfide core during long-term charging and discharging. , to ensure the stability of the material structure; using it as a negative electrode material for sodium-ion batteries can improve battery capacity and battery cycle stability.
(2)本发明提供的制备方法，采用三步法即可，制备方法简单，能够得到形貌均一可控的硫化镍复合材料。(2) The preparation method provided by the present invention can adopt a three-step method, the preparation method is simple, and a nickel sulfide composite material with uniform and controllable morphology can be obtained.
附图说明Description of drawings
图1为实施例1制得的硫化镍复合材料的SEM图；Fig. 1 is the SEM image of the nickel sulfide composite material obtained in Example 1;
图2为对比例1制得的NiS2微球的SEM图；Fig. 2 is the SEM image of NiS 2 microspheres obtained in Comparative Example 1;
图3为实施例1制得的硫化镍复合材料和对比例1制得的NiS2微球的XRD图；3 is the XRD pattern of the nickel sulfide composite material prepared in Example 1 and the NiS 2 microspheres prepared in Comparative Example 1;
图4为应用例1制得的电池的伏安循环曲线图；Fig. 4 is the voltammetric cycle curve diagram of the battery that application example 1 makes;
图5为应用例1和对比例2制得的电池的倍率性能图；Fig. 5 is the rate performance diagram of the battery prepared by Application Example 1 and Comparative Example 2;
图6为应用例1和对比例2制得的电池的循环性能图。FIG. 6 is a graph showing the cycle performance of the batteries prepared in Application Example 1 and Comparative Example 2. FIG.
具体实施方式Detailed ways
为了让本领域技术人员更加清楚明白本发明所述技术方案，现列举以下实施例进行说明。需要指出的是，以下实施例对本发明要求的保护范围不构成限制作用。In order to make those skilled in the art understand the technical solutions of the present invention more clearly, the following examples are now given for illustration. It should be pointed out that the following examples do not limit the protection scope of the present invention.
以下实施例中所用的原料、试剂或装置如无特殊说明，均可从常规商业途径得到，或者可以通过现有已知方法得到。The raw materials, reagents or devices used in the following examples can be obtained from conventional commercial channels unless otherwise specified, or can be obtained by existing known methods.
实施例1Example 1
一种核壳结构的氮掺杂碳包覆的硫化镍复合材料，其制备方法包括如下步骤：A core-shell structure nitrogen-doped carbon-coated nickel sulfide composite material, the preparation method comprising the following steps:
(1)按0.02mol L-1的浓度将四水乙酸镍以及2％(相对四水乙酸镍摩尔质量)的十六烷基二甲基溴化铵均匀溶解在甲醇溶剂中，转移到聚四氟乙烯内衬中，将内衬装入水热外釜固定密封，在180℃下溶剂热反应48h。反应结束后冷却至室温，用乙醇离心洗涤三次，在60℃下真空干燥12h后得到前驱体，即羟甲基氢氧化镍Ni(OH)(OCH3)。(1) Uniformly dissolve nickel acetate tetrahydrate and 2% (relative molar mass of nickel acetate tetrahydrate) in methanol solvent at a concentration of 0.02 mol L- 1 , transfer to polytetrafluoroethylene In the vinyl fluoride lining, the lining was put into a hydrothermal outer kettle to be fixed and sealed, and the solvothermal reaction was carried out at 180 °C for 48 h. After the reaction was completed, it was cooled to room temperature, washed with ethanol for three times by centrifugation, and vacuum-dried at 60° C. for 12 h to obtain the precursor, namely hydroxymethyl nickel hydroxide Ni(OH)(OCH 3 ).
(2)配制100mL浓度为0.01mol L-1的Tris溶液，准确称量100mg前驱体利用超声均匀分散于Tris溶液中。随后，在搅拌状态下称取50mg盐酸多巴胺加入上述Tris溶液中，溶液保持搅拌反应24h(原位聚合处理)。最后离心、洗涤，60℃下真空干燥12h得到包覆体，记作Ni(OH)(OCH3)@PDA。(2) 100 mL of Tris solution with a concentration of 0.01 mol L- 1 was prepared, and 100 mg of the precursor was accurately weighed and uniformly dispersed in the Tris solution by ultrasound. Subsequently, 50 mg of dopamine hydrochloride was weighed and added to the above Tris solution under stirring, and the solution was kept stirring for 24 hours (in-situ polymerization treatment). Finally, centrifuge, wash, and vacuum dry at 60 °C for 12 h to obtain a coating, which is denoted as Ni(OH)(OCH 3 )@PDA.
(3)将0.2g升华硫与0.1g Ni(OH)(OCH3)@PDA装入小瓷舟，分别放置管式炉两端，升华硫靠近于进气口端。在氮气气氛中，于350℃煅烧2h，最终得到具有核壳结构的硫化镍复合材料(标记为NiSx@NC)。(3) Load 0.2 g of sublimation sulfur and 0.1 g of Ni(OH)(OCH 3 )@PDA into a small porcelain boat, and place the two ends of the tube furnace respectively, with the sublimated sulfur close to the gas inlet. After calcination at 350 °C for 2 h in a nitrogen atmosphere, a nickel sulfide composite with a core-shell structure (marked as NiS x @NC) was finally obtained.
应用例1Application example 1
将实施例1制得的硫化镍复合材料作为钠离子电池负极材料，并制备电池。The nickel sulfide composite material prepared in Example 1 was used as the negative electrode material of the sodium ion battery, and the battery was prepared.
具体步骤如下：将实施例1制得的硫化镍复合材料(NiSx@NC)与乙炔黑、聚偏氟乙烯按照质量比7：2：1混合，以N-甲基吡咯烷酮为溶剂研磨制成浆料，将浆料涂布到铜箔表面，在60℃的真空干燥箱中干燥12h，即可制得所述钠离子电池负极片。The specific steps are as follows: the nickel sulfide composite material (NiS x @NC) prepared in Example 1 is mixed with acetylene black and polyvinylidene fluoride according to a mass ratio of 7:2:1, and is prepared by grinding with N-methylpyrrolidone as a solvent. The slurry is coated on the surface of the copper foil and dried in a vacuum drying oven at 60° C. for 12 hours to prepare the negative electrode sheet of the sodium ion battery.
以金属钠片作为正极片，以浓度为1mol L-1六氟磷酸钠为电解液，以乙二醇二甲醚为溶剂，在手套箱中将正极壳、正极片、弹片、垫片、隔膜、负极片、负极壳并滴加适量电解液组装成扣式电池。此过程为常规技术，不做过多介绍。Using sodium metal sheet as the positive electrode sheet, with a concentration of 1mol L- 1 sodium hexafluorophosphate as the electrolyte, with ethylene glycol dimethyl ether as the solvent, the positive electrode shell, positive electrode sheet, shrapnel, gasket, diaphragm in the glove box. , a negative electrode sheet, a negative electrode shell and an appropriate amount of electrolyte are added dropwise to assemble a button battery. This process is a conventional technique and will not be introduced too much.
对比例1Comparative Example 1
本对比例提供一种NiS2微球，相较实施例1没有进行盐酸多巴胺原位聚合处理。This comparative example provides a NiS 2 microsphere, which is not subjected to in-situ polymerization of dopamine hydrochloride compared to Example 1.
具体地，本对比例的NiS2微球的制备方法包括如下步骤：Specifically, the preparation method of the NiS 2 microspheres of this comparative example comprises the following steps:
(1)按0.02mol L-1的浓度将四水乙酸镍以及2％(相对四水乙酸镍摩尔量)的表面活性剂均匀溶解在甲醇溶剂中，转移到聚四氟乙烯内衬中，将内衬装入水热外釜固定密封，在180℃下溶剂热反应48h。反应结束后冷却至室温，用乙醇离心洗涤三次，在60℃下真空干燥12h后得到前驱体，即羟甲基氢氧化镍Ni(OH)(OCH3)。(1) Uniformly dissolve nickel acetate tetrahydrate and 2% (relative molar amount of nickel acetate tetrahydrate) in methanol solvent at a concentration of 0.02 mol L- 1 , transfer to a polytetrafluoroethylene lining, The inner lining was placed in a hydrothermal outer kettle to be fixed and sealed, and the solvothermal reaction was carried out at 180 °C for 48 h. After the reaction was completed, it was cooled to room temperature, washed with ethanol for three times by centrifugation, and vacuum-dried at 60° C. for 12 h to obtain the precursor, namely hydroxymethyl nickel hydroxide Ni(OH)(OCH 3 ).
(2)按质量比为2:1将0.2g升华硫与0.1g Ni(OH)(OCH3)装入小瓷舟，分别放置管式炉两端，升华硫靠近于进气口端。在氮气气氛中，于350℃煅烧2h，最终得到NiS2微球。(2) Load 0.2 g of sublimated sulfur and 0.1 g of Ni(OH)(OCH 3 ) into a small porcelain boat at a mass ratio of 2:1, and place the two ends of the tube furnace respectively, with the sublimated sulfur close to the air inlet. In a nitrogen atmosphere, calcined at 350 °C for 2 h to finally obtain NiS 2 microspheres.
对比例2Comparative Example 2
将对比例1制得的硫化复合材料作为钠离子电池负极材料，并制备电池。The vulcanized composite material prepared in Comparative Example 1 was used as the anode material of sodium ion battery, and the battery was prepared.
具体步骤如下：将对比例1制得的NiS2微球与乙炔黑、聚偏氟乙烯按照质量比7：2：1混合，以N-甲基吡咯烷酮为溶剂研磨制成浆料，将浆料涂布到铜箔表面，在60℃的真空干燥箱中干燥12h，即可制得所述钠离子电池负极片。The specific steps are as follows: the NiS 2 microspheres prepared in Comparative Example 1 are mixed with acetylene black and polyvinylidene fluoride in a mass ratio of 7:2:1, and N-methylpyrrolidone is used as a solvent to grind to prepare a slurry. The negative electrode sheet of the sodium ion battery can be prepared by coating it on the surface of the copper foil and drying it in a vacuum drying oven at 60° C. for 12 hours.
以金属钠片作为正极片，以浓度为1mol L-1六氟磷酸钠为电解液，以乙二醇二甲醚为溶剂，在手套箱中将正极壳、正极片、弹片、垫片、隔膜、负极片、负极壳并滴加适量电解液组装成扣式电池。此过程为常规技术，不做过多介绍。Using sodium metal sheet as the positive electrode sheet, with a concentration of 1mol L- 1 sodium hexafluorophosphate as the electrolyte, with ethylene glycol dimethyl ether as the solvent, the positive electrode shell, positive electrode sheet, shrapnel, gasket, diaphragm in the glove box. , a negative electrode sheet, a negative electrode shell and an appropriate amount of electrolyte are added dropwise to assemble a button battery. This process is a conventional technique and will not be introduced too much.
产品效果测试Product effect test
(1)形貌表征：(1) Morphological characterization:
对实施例1制得的硫化镍复合材料(NiSx@NC)和对比例1制得的NiS2微球进行扫描电镜分析。硫化镍复合材料(NiSx@NC)的微观形貌如图1所示。图1中a和b分别代表不同分辨率下硫化镍复合材料(NiSx@NC)的SEM图。由图1可知，本发明提供的硫化镍复合材料(NiSx@NC)具有均一的三维球状的微观形貌，同时，该球状颗粒具有核壳结构，包括内核和外壳，内核粒径为1-1.5μm，外壳厚度为100-150nm。Scanning electron microscope analysis was performed on the nickel sulfide composite material (NiS x @NC) prepared in Example 1 and the NiS 2 microspheres prepared in Comparative Example 1. The microstructure of the nickel sulfide composite (NiS x @NC) is shown in Figure 1. In Figure 1, a and b represent the SEM images of the nickel sulfide composite (NiS x @NC) at different resolutions, respectively. It can be seen from FIG. 1 that the nickel sulfide composite material (NiS x @NC) provided by the present invention has a uniform three-dimensional spherical microscopic morphology, and at the same time, the spherical particles have a core-shell structure, including an inner core and an outer shell, and the inner core particle size is 1- 1.5μm, the shell thickness is 100-150nm.
NiS2微球的形貌如图2所示，图2中a和b分别代表不同分辨率下NiS2微球的SEM图。对比图1可知，没有进行氮掺杂和碳包覆处理的NiS2微球没有核壳结构，且有破碎，表明在硫化过程中容易高温破碎。The morphologies of the NiS 2 microspheres are shown in Fig. 2, and a and b in Fig. 2 represent the SEM images of the NiS 2 microspheres at different resolutions, respectively. Compared with Fig. 1, it can be seen that the NiS 2 microspheres without nitrogen doping and carbon coating treatment have no core-shell structure and are broken, indicating that they are easily broken at high temperature during the vulcanization process.
对实施例1制得的硫化镍复合材料(NiSx@NC)和对比例1制得的NiS2微球进行X射线衍射分析。图3为硫化镍复合材料(NiSx@NC)和NiS2微球的XRD图，图3中曲线分别代表硫化镍(PDF#02-1298)、二硫化镍(PDF#11-0099)、NiS2微球和硫化镍复合材料(NiSx@NC)。硫化镍复合材料(NiSx@NC)的衍射峰与硫化镍的PDF#02-1298卡片以及二硫化镍的PDF#11-0099卡片一一对应，结合图1可以说明本发明成功制得核壳结构的硫化镍微球。X-ray diffraction analysis was performed on the nickel sulfide composite material (NiS x @NC) prepared in Example 1 and the NiS 2 microspheres prepared in Comparative Example 1. Figure 3 shows the XRD patterns of nickel sulfide composites (NiS x @NC) and NiS 2 microspheres. The curves in Figure 3 represent nickel sulfide (PDF#02-1298), nickel disulfide (PDF#11-0099), NiS 2 microspheres and nickel sulfide composite (NiS x @NC). The diffraction peaks of the nickel sulfide composite material (NiS x @NC) correspond to the PDF#02-1298 card of nickel sulfide and the PDF#11-0099 card of nickel disulfide one by one. Combining with Figure 1, it can be shown that the core-shell obtained by the present invention is successful. Structure of nickel sulfide microspheres.
(2)电化学性能测试：(2) Electrochemical performance test:
对应用例1和对比例2制备的电池分别进行电化学性能测试。图4为应用例1制得的电池在0.1mV·s-1时的伏安循环曲线图，其中横坐标为电位，纵坐标为电流。由图4可知，应用例1制得的电池在第一圈的循环伏安扫描中，阴极扫描时于1.24V有一个强度较高的还原峰，对应的是SEI膜的形成。在接下来的扫描中，两对氧化/还原峰1.72V/1.44V和1.96V/0.91V分别对应的是转化反应
图5为应用例1和对比例2制得的电池的倍率性能图，其中横坐标为循环序号，纵坐标为比容量，图5中曲线分别代表应用例1制得的电池(NiSx@NC)和对比例2制得的电池(NiS2)在电流密度为1-5A g-1时的倍率性能图。由图5可知，在0.1、0.2、0.5、1、2A g-1的电流密度下，硫化镍复合材料(NiSx@NC)制得的电池分别具有401.5、389.6、375.6、346.8、318.9mA h g-1的高放电比容量。甚至当电流密度为5A g-1时，仍然具有297.2mA h g-1的放电比容量。而材料在未进行碳包覆时，对比例2制得的电池(NiS2)在0.1-5A g-1的电流密度下的放电比容量仅为243.2、201.6、198.6、184.3、176.2mA h g-1，均低于应用例1制得的电池，说明NiS2微球作为电池负极材料的性能远差于硫化镍复合材料(NiSx@NC)。Figure 5 is a graph of the rate performance of the batteries prepared in Application Example 1 and Comparative Example 2, where the abscissa is the cycle number and the ordinate is the specific capacity. The curves in Figure 5 represent the batteries (NiS x @NC) prepared in Application Example 1 respectively. ) and the battery (NiS 2 ) prepared in Comparative Example 2 at current densities of 1-5 A g- 1 . It can be seen from Figure 5 that at the current densities of 0.1, 0.2, 0.5, 1, and 2 A g- 1 , the batteries made of nickel sulfide composites (NiS x @NC) have 401.5, 389.6, 375.6, 346.8, and 318.9 mA h, respectively. The high discharge specific capacity of g- 1 . Even when the current density is 5A g- 1 , it still has a discharge specific capacity of 297.2 mA h g- 1 . When the material is not coated with carbon, the discharge specific capacity of the battery (NiS 2 ) prepared in Comparative Example 2 is only 243.2, 201.6, 198.6, 184.3, 176.2 mA h g at the current density of 0.1-5A g- 1 - 1 , all lower than the battery prepared in Application Example 1, indicating that the performance of NiS 2 microspheres as a battery anode material is far worse than that of the nickel sulfide composite material (NiS x @NC).
最后，循环稳定性是电池应用的重大阻碍，尤其是钠离子电池。因此，本发明也探究了应用例1和对比例2制得的电池的循环稳定性，在1A g-1的电流密度下进行循环测试。图6为应用例1(NiSx@NC)和对比例2(NiS2)制得的电池的循环性能图，其中横坐标为循环序号，纵坐标为比容量。由图6可知，在100圈循环后，应用例1(NiSx@NC)制得的电池仍然表现出较高的放电比容量(368.4mA h g-1)，保持在首圈的98.68％。而由未进行碳包覆的NiS2微球制备的电池在1A g-1的电流密度下循环100圈后，仅表现出148.6mA h g-1的放电比容量，保持率仅为56％；并且，与应用例1(NiSx@NC)制得的电池相比，其比容量降低了50％。可见，通过碳包覆处理进行复合，可有效改善NiS2微球的微观形貌，使其更有利于离子和电子传输，从而提高其比容量以及循环稳定性。Finally, cycling stability is a significant impediment to battery applications, especially for Na-ion batteries. Therefore, the present invention also explores the cycle stability of the batteries prepared in Application Example 1 and Comparative Example 2, and conducts a cycle test at a current density of 1A g- 1 . Fig. 6 is a cycle performance diagram of the batteries prepared in Application Example 1 (NiS x @NC) and Comparative Example 2 (NiS 2 ), wherein the abscissa is the cycle number, and the ordinate is the specific capacity. It can be seen from Figure 6 that after 100 cycles, the battery prepared in Application Example 1 (NiS x @NC) still showed a higher discharge specific capacity (368.4 mA hg -1 ), which was maintained at 98.68% of the first cycle. However, the battery prepared from the uncoated NiS 2 microspheres exhibited only a discharge specific capacity of 148.6 mA hg -1 after 100 cycles at a current density of 1 A g -1 with a retention rate of only 56%; and , compared with the battery prepared in Application Example 1 (NiS x @NC), its specific capacity was reduced by 50%. It can be seen that the composite through carbon coating treatment can effectively improve the microscopic morphology of NiS 2 microspheres, making them more conducive to ion and electron transport, thereby improving their specific capacity and cycle stability.
过渡金属硫化物在钠离子电池中的充放电机理与在锂离子电池类似，主要是通过转化反应。虽然过渡金属硫化物具有较高的理论容量(例如NiS：约为590mA h g-1，NiS2：约为879mA h g-1)，然而，由于转化反应会引起较大的体积膨胀效应，导致材料粉化，进而导致容量急剧下降。此外，在充放电过程中，过渡金属硫化物往往会生成中间产物(多聚硫化物)，中间产物容易溶于电解液中，导致电池容量降低。因此，本发明通过氮掺杂的碳壳进行包覆，形成具有核壳结构的硫化镍复合材料，可以从至少以下三个方面提升材料的电化学性能：①氮掺杂的碳壳能有效提高电子、钠离子的扩散速率，从而提高材料的倍率性能；②氮掺杂的碳壳作为保护层，通过抑制材料在长期循环中引起的不可避免的体积膨胀，保护材料的微观形貌和结构；③氮掺杂的碳壳作为隔离层，减少中间产物与电解液直接接触。因此，相比NiS2材料，NiSx@NC表现出更高的倍率性能和循环稳定性能。The charge-discharge mechanism of transition metal sulfides in Na-ion batteries is similar to that in Li-ion batteries, mainly through conversion reactions. Although transition metal sulfides have higher theoretical capacities (eg NiS: about 590 mA hg -1 , NiS 2 : about 879 mA hg -1 ), however, due to the large volume expansion effect caused by the conversion reaction, the material powder , resulting in a sharp drop in capacity. In addition, during the charging and discharging process, transition metal sulfides often generate intermediate products (polysulfides), which are easily dissolved in the electrolyte, resulting in a decrease in battery capacity. Therefore, the present invention is coated with a nitrogen-doped carbon shell to form a nickel sulfide composite material with a core-shell structure, which can improve the electrochemical performance of the material from at least the following three aspects: ① The nitrogen-doped carbon shell can effectively improve the The diffusion rate of electrons and sodium ions can improve the rate performance of the material; ② The nitrogen-doped carbon shell acts as a protective layer to protect the microscopic morphology and structure of the material by suppressing the inevitable volume expansion caused by the material during long-term cycling; ③ The nitrogen-doped carbon shell acts as a separator to reduce the direct contact between the intermediate product and the electrolyte. Therefore, NiS x @NC exhibits higher rate capability and cycling stability than NiS materials.
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