CN117996057A - Negative electrode material and preparation method and application thereof - Google Patents
Negative electrode material and preparation method and application thereof Download PDFInfo
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- CN117996057A CN117996057A CN202410397301.6A CN202410397301A CN117996057A CN 117996057 A CN117996057 A CN 117996057A CN 202410397301 A CN202410397301 A CN 202410397301A CN 117996057 A CN117996057 A CN 117996057A
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010405 anode material Substances 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000010335 hydrothermal treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- PKPDMQHIYXYXTQ-UHFFFAOYSA-N [Ni].NN Chemical compound [Ni].NN PKPDMQHIYXYXTQ-UHFFFAOYSA-N 0.000 claims description 10
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000010306 acid treatment Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000002073 nanorod Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 8
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 239000002620 silicon nanotube Substances 0.000 description 49
- 229910021430 silicon nanotube Inorganic materials 0.000 description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- -1 provides tin ions Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- LQJIDIOGYJAQMF-UHFFFAOYSA-N lambda2-silanylidenetin Chemical compound [Si].[Sn] LQJIDIOGYJAQMF-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QBWXYICYWNSGPT-UHFFFAOYSA-L dichlorotin pentahydrate Chemical compound O.O.O.O.O.Cl[Sn]Cl QBWXYICYWNSGPT-UHFFFAOYSA-L 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a negative electrode material, a preparation method and application thereof, wherein the negative electrode material comprises SNTs@Sn, and Sn in the SNTs@Sn is coated on the inner wall and the outer wall of the SNTs. The invention provides a negative electrode material comprising SNTs@Sn, wherein the SNTs@Sn is modified by adopting metal Sn, so that the conductivity of a battery prepared from the negative electrode material is improved, the ion diffusion path of the battery is shortened, the initial discharge/charge specific capacity of the battery is improved, the volume expansion rate of the battery is reduced, and the battery has higher cycling stability.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a negative electrode material, and a preparation method and application thereof.
Background
SiO 2 cathode attracts wide attention because of its higher lithium intercalation capacity (1965 mAh/g), excellent cycle stability, easy synthesis, low cost and other advantages. However, siO 2 is known to have a certain volume expansion and a low electron conductivity, so that the wide use in industry is limited, and the combination of SiO 2 with other materials provides a method for solving the dilemma of silicon dioxide.
CN115188919a discloses a negative electrode sheet, a preparation method and a battery thereof. The negative electrode plate comprises a current collector, and a lithium metal layer and a composite silicon negative electrode layer which are sequentially laminated on at least one surface of the current collector, wherein the composite silicon negative electrode layer is composed of a negative electrode material and a fiber layer embedded in the negative electrode material, and the negative electrode material comprises a silicon-based negative electrode material. But the battery prepared with the negative electrode material has low conductivity and low cycle stability due to volume expansion.
CN106848182a discloses a method for manufacturing a lithium ion battery negative electrode plate, which comprises the following steps: step one: taking a negative current collector, and carrying out surface pretreatment on the negative current collector; step two: taking a certain amount of mixture powder of a tin-based material and a silicon-based material, adding a binder to prepare paste, forming a negative electrode active substance, and coating the obtained negative electrode active substance on a negative electrode current collector to obtain a primary negative electrode material; step three: and (3) carrying out surface laser melting on the primary negative electrode material prepared in the step (II), and forming a cladding layer on the surface of the primary negative electrode material to obtain the tin-silicon composite film negative electrode plate. Step four: and (3) carrying out heat treatment on the tin-silicon composite film negative electrode plate obtained in the step (III) to obtain the final composite material negative electrode plate. But the conductivity of the anode material is low.
The composite material of SiO 2 and other materials disclosed at present has certain defects, and the problems that the conductivity of a battery prepared by the composite material is poor, the initial coulomb efficiency is low, and the cycling stability is low due to volume expansion exist. Therefore, development and design of a novel anode material and a preparation method thereof are important.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a negative electrode material, a preparation method and application thereof, and the invention provides a negative electrode material comprising SNTs@Sn, wherein the SNTs@Sn is modified by adopting metal Sn, so that the conductivity of a battery prepared from the negative electrode material is improved, the ion diffusion path of the battery is shortened, the initial discharge/charge specific capacity of the battery is improved, the volume expansion rate of the battery is reduced, and the battery has higher cycling stability.
To achieve the purpose, the invention adopts the following technical scheme:
In a first aspect, the invention provides a negative electrode material, which comprises SNTs@Sn, wherein Sn in the SNTs@Sn is coated on the inner wall and the outer wall of the SNTs.
The metal Sn in the metal material has higher theoretical lithium storage capacity (994 mAh/g) and lower lithium ion deintercalation platform voltage, is considered as a potential lithium ion battery cathode material candidate, and the doping of Sn can not only enhance the conductivity of silicon, but also reduce the volume expansion rate of silicon.
The tubular structure of the Silicon Nanotubes (SNTs) is beneficial to providing rich active sites in the battery by the cathode material, shortening the ion diffusion path, facilitating electron transmission and ion diffusion, and has great significance for improving the first effect of the battery.
Therefore, the invention provides the negative electrode material comprising SNTs@Sn, and the SNTs are modified by adopting the metal Sn, so that the conductivity of the battery prepared by the negative electrode material is improved, the ion diffusion path of the battery is shortened, the initial discharge/charge specific capacity of the battery is improved, the volume expansion rate of the battery is reduced, and the battery has higher cycle stability.
Preferably, the existence form of Sn in the SNTs@Sn is tetrahedral coordination configuration, and the tetrahedral coordination configuration is favorable for realizing the tight combination of Sn-O-Si chemical bonds in the SNTs@Sn, so that the initial discharge/charge specific capacity, the reversible capacity after charge and discharge cycles, the coulombic efficiency and the reversible lithium storage capacity of the battery are improved.
Preferably, the molar ratio of Si to Sn in the snts@sn is (5 to 15): 1, for example, it may be 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1 or 15:1, but not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable, preferably (8 to 12): 1; when the molar ratio of Si to Sn is lower, the specific surface area of SNTs@Sn is reduced, the electrochemical performance is reduced, and the conductivity is poor; when the molar ratio of Si to Sn is higher, the specific surface area of SNTs@Sn is increased, the pore volume is also changed, the improvement of the performance of the anode material is not facilitated, and the production cost of the anode material is increased due to the excessively high Sn content.
Preferably, the SNTs in the SNTs@Sn are of a structure with micropores and mesopores coexisting, and the SNTs of the micropores and the mesopores are beneficial to the distribution of active sites, so that the contact and the transmission of ions or electrolyte molecules are facilitated.
In a second aspect, the present invention provides a method for preparing the anode material according to the first aspect, the method comprising:
and synthesizing a precursor on the surface of the template by adopting an in-situ synthesis method, removing the template, and then carrying out reduction treatment to obtain SNTs@Sn.
The preparation method of the anode material provided by the invention is simple to operate, low in cost and beneficial to commercial production.
Preferably, the template is a nickel hydrazine complex template.
The nickel hydrazine complex template is prepared by adopting a method in the prior art, the preparation of the nickel hydrazine complex template is not limited, and any method capable of preparing the nickel hydrazine complex template can be applied.
Preferably, the nickel hydrazine complex template is Ni-N 2H4, but is not limited to Ni-N 2H4, and other nickel hydrazine complex templates in the prior art are applicable.
Preferably, the in situ synthesis method comprises hydrolyzing the organosilicon compound and the water-soluble tin salt at the surface of the template.
Preferably, the hydrolyzed organosilicon compound is any one or a combination of at least two of tetraethyl silicate, tetraethyl orthosilicate, or methyl silicate, and typical, but non-limiting, combinations include a combination of tetraethyl silicate and tetraethyl orthosilicate, a combination of ethyl silicate and methyl silicate, or a combination of tetraethyl silicate, tetraethyl orthosilicate, and methyl silicate.
The water-soluble tin salt is common organic or inorganic tin salt, mainly provides tin ions, and theoretically, the water-soluble tin salt with hydrolytic property meets the use requirement.
Preferably, the water-soluble tin salt is any one or a combination of at least two of tin tetrachloride, tin tetrachloride pentahydrate or stannous chloride, and typical but non-limiting combinations include a combination of tin tetrachloride and tin tetrachloride pentahydrate, a combination of tin tetrachloride and stannous chloride pentahydrate, or a combination of tin tetrachloride, tin tetrachloride pentahydrate and stannous chloride.
Preferably, the removing the template includes treatment with an acid.
Preferably, the acid used for the acid treatment comprises hydrochloric acid.
The concentration of the hydrochloric acid is preferably 0.5 to 1.5mol/L, for example, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L or 1.5mol/L, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical ranges are equally applicable.
Preferably, the acid treatment is performed for 5 to 7 days, for example, 5 days, 5.2 days, 5.4 days, 5.6 days, 5.8 days, 6 days, 6.2 days, 6.4 days, 6.6 days, 6.8 days or 7 days, but the acid treatment is not limited to the listed values, and other non-listed values within the range are applicable.
Preferably, the reduction treatment comprises a hydrothermal treatment followed by a heat treatment in a protective atmosphere.
The invention also comprises centrifugation and drying which are sequentially carried out between the hydrothermal treatment and the heat treatment.
Preferably, the temperature of the hydrothermal treatment is 150-190 ℃ and the time is 4-8 hours.
The temperature of the hydrothermal treatment in the present invention is 150 to 190 ℃, and may be, for example, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, or 190 ℃, but is not limited to the values listed, and other values not listed in the range are equally applicable; when the temperature of the hydrothermal treatment is lower, the dissolution of reactants and the crystallization of products are affected, and the growth and the formation of an SNTs@Sn structure are not facilitated; when the temperature of the hydrothermal treatment is higher, the particle size of the metal Sn is increased, so that the electrochemical performance of SNTs@Sn is affected.
The time of the hydrothermal treatment in the present invention is 4 to 8 hours, and may be, for example, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours or 8 hours, but the present invention is not limited to the recited values, and other values not recited in the range of the values are equally applicable.
Preferably, the heat treatment includes sequentially heating and insulating.
Preferably, the temperature rising rate is 1-5 ℃ min -1, and the end point temperature is 600-1000 ℃.
The rate of temperature increase in the present invention is 1 to 5℃min -1, and may be 1℃·min-1、1.5℃·min-1、2℃·min-1、2.5℃·min-1、3℃·min-1、3.5℃·min-1、4℃·min-1、4.5℃·min-1 or 5℃min -1, for example, but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are applicable.
The temperature at the end of the temperature rise in the present invention is a temperature at which the temperature is kept, and the temperature at the end of the temperature rise in the present invention is 600 to 800 ℃, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃ or 800 ℃, but the temperature at the end of the temperature rise is not limited to the listed values, and other non-listed values in the range of the values are equally applicable; when the temperature of the heat preservation is low, sn exists in a SnO 2 state, which is not beneficial to improving the electrochemical performance of the anode material; when the temperature of the heat preservation is higher, sn is easy to sinter and agglomerate, blocks pore channels, is unfavorable for uniform loading of Sn, and is unfavorable for improving the electrochemical performance of the anode material.
Preferably, the time for the heat preservation is 1 to 3 hours, for example, 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, 2 hours, 2.2 hours, 2.4 hours, 2.6 hours, 2.8 hours or 3 hours, but the heat preservation is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
Hydrolyzing the surface of the Ni-N 2H4 nano rod to synthesize a precursor, performing acid treatment by adopting hydrochloric acid to remove a template, performing hydrothermal treatment at 150-190 ℃ for 4-8 hours, heating to 600-800 ℃ in a protective atmosphere at the heating rate of 1-5 ℃ min -1, and then preserving heat for 1-3 hours to obtain SNTs@Sn.
In a third aspect, the present invention provides a negative electrode tab comprising the negative electrode material of the first aspect.
In a fourth aspect, the present invention provides a battery comprising the negative electrode tab of the third aspect.
The battery comprises the negative electrode plate prepared from the negative electrode material in the first aspect, and the negative electrode material provides rich active sites in the battery, shortens an ion diffusion path, is beneficial to electron transmission and ion transmission, and therefore improves the initial discharge/charge specific capacity of the battery.
Compared with the prior art, the invention has the following beneficial effects:
The invention provides a negative electrode material comprising SNTs@Sn, wherein the SNTs@Sn is modified by adopting metal Sn, so that the conductivity of a battery prepared from the negative electrode material is improved, the ion diffusion path of the battery is shortened, the initial discharge/charge specific capacity of the battery is improved, the volume expansion rate of the battery is reduced, and the battery has higher cycling stability.
Drawings
Fig. 1 is an isothermal desorption curve of the anode materials in examples 1, 4, and 5.
Fig. 2 is an X-ray diagram of the anode material in examples 1, 4 and 5.
Fig. 3 is an X-ray energy spectrum of the anode material in examples 1, 4 and 5.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a negative electrode material, which comprises SNTs@Sn, wherein Sn in the SNTs@Sn is coated on the inner wall and the outer wall of the SNTs, the existence form of the Sn is in a tetrahedral coordination configuration, and the molar ratio of Si to Sn is 8:1.
The preparation method of the anode material comprises the following steps:
(1) Synthesizing a precursor on the surface of the nickel hydrazine complex template by adopting an in-situ synthesis method:
8.5g of polyoxyethylene hexadecane ether is placed in a three-hole flask, 15mL of n-butanol is used for dissolution, the flask is placed in a water bath kettle at 50 ℃ for stirring, after the solid is completely dissolved, 1.7mL of 0.8mol/L nickel chloride solution is slowly added, 1.5h later, 1mL of ethylenediamine and 50 mu L of 3-aminopropyl triethoxysilane are added, stirring is carried out for 2h later, then 3mL of tetraethyl silicate with the mass fraction of 99.99wt% and 70 mg of tin tetrachloride pentahydrate are added, and the molar ratio of Si in the tetraethyl silicate to Sn in the tin tetrachloride pentahydrate is 8:1.
(2) Removing the template:
Adding 30mL of 1 mol/L hydrochloric acid into the solution in the step (1), soaking for 1 day, centrifuging, removing the supernatant (namely removing the hydrochloric acid), adding 30mL of 1 mol/L hydrochloric acid again, soaking for 1 day, centrifuging, removing the supernatant (namely removing the hydrochloric acid), and repeating the steps for 7 times until the solution in the step (1) is changed from blue to colorless.
(3) Reducing to obtain SNTs@Sn:
pouring the solution obtained in the step (2) into a hydrothermal reaction kettle, and preserving heat in an oven at 180 ℃ for 6 h; then centrifuging and drying; and placing the dried mixture into a crucible, and setting a tube furnace to be heated to 800 ℃ with a program of -1 ℃ in a 2 ℃ min under the argon atmosphere, and preserving heat for 1h to obtain the SNTs@Sn material.
Example 2
The embodiment provides a negative electrode material, which comprises SNTs@Sn, wherein Sn in the SNTs@Sn is coated on the inner wall and the outer wall of the SNTs, the existence form of the Sn is a tetrahedral coordination compound, and the molar ratio of Si to Sn is 10:1.
The preparation method of the anode material comprises the following steps:
(1) Synthesizing a precursor on the surface of the nickel hydrazine complex template by adopting an in-situ synthesis method:
8.5g of polyoxyethylene hexadecane ether was placed in a three-hole flask, dissolved with 15mL of n-butanol, the flask was placed in a water bath at 50℃and stirred, after the solid was completely dissolved, 1.7mL of a 0.8mol/L nickel chloride solution was slowly added, after 1.5h, 1mL of ethylenediamine and 50. Mu.L of 3-aminopropyl triethoxysilane were added and stirred for 2h, then 3mL of tetraethyl silicate having a mass fraction of 99.99% wt and 59mg of tin tetrachloride pentahydrate having a molar ratio of Sn in Si pentahydrate tin tetrachloride of 10:1 were added.
(2) Removing the template:
Adding 30mL of 1 mol/L hydrochloric acid into the solution in the step (1), soaking for 1 day, centrifuging, removing the supernatant (namely removing the hydrochloric acid), adding 30mL of 1 mol/L hydrochloric acid again, soaking for 1 day, centrifuging, removing the supernatant (namely removing the hydrochloric acid), and repeating the steps for 7 times until the solution in the step (1) is changed from blue to colorless.
(3) Reducing to obtain SNTs@Sn:
pouring the solution obtained in the step (2) into a hydrothermal reaction kettle, and preserving heat in an oven at 160 ℃ for 8 h; then centrifuging and drying; and placing the dried mixture into a crucible, and setting a tube furnace to be heated to 600 ℃ in a program of -1 ℃ in 3 ℃ under the argon atmosphere, and preserving heat for 3h to obtain the SNTs@Sn material.
Example 3
The embodiment provides a negative electrode material, which comprises SNTs@Sn, wherein Sn in the SNTs@Sn is coated on the inner wall and the outer wall of the SNTs, the existence form of the Sn is a tetrahedral coordination compound, and the molar ratio of Si to Sn is 12:1.
The preparation method of the anode material comprises the following steps:
(1) Synthesizing a precursor on the surface of the nickel hydrazine complex template by adopting an in-situ synthesis method:
8.5g of polyoxyethylene hexadecane ether was placed in a three-hole flask, dissolved with 15mL of n-butanol, the flask was placed in a water bath at 50℃and stirred, after the solid was completely dissolved, 1.7mL of a 0.8mol/L nickel chloride solution was slowly added, after 1.5h, 1mL of ethylenediamine and 50. Mu.L of 3-aminopropyl triethoxysilane were added and stirred for 2h, then 3mL of tetraethyl silicate having a mass fraction of 99.99% wt and 49mg of tin tetrachloride pentahydrate having a Si to Sn molar ratio of 12:1 in tin tetrachloride pentahydrate were added.
(2) Removing the template:
Adding 30mL of 1 mol/L hydrochloric acid into the solution in the step (1), soaking for 1 day, centrifuging, removing the supernatant (namely removing the hydrochloric acid), adding 30mL of 1 mol/L hydrochloric acid again, soaking for 1 day, centrifuging, removing the supernatant (namely removing the hydrochloric acid), and repeating the steps for 7 times until the solution in the step (1) is changed from blue to colorless.
(3) Reducing to obtain SNTs@Sn:
Pouring the solution obtained in the step (2) into a hydrothermal reaction kettle, and preserving heat in an oven at 170 ℃ to 7 h; then centrifuging and drying; and placing the dried mixture into a crucible, and setting a tube furnace to be heated to 700 ℃ in a program of -1 ℃ in 4 ℃ under the argon atmosphere, and preserving heat for 2h to obtain the SNTs@Sn material.
Example 4
This example provides a negative electrode material that is the same as example 1 except that the molar ratio of Si to Sn in the snts@sn is 5:1.
Example 5
This example provides a negative electrode material that is the same as example 1 except that the molar ratio of Si to Sn in the snts@sn is 15:1.
Example 6
This example provides a negative electrode material that is the same as example 1 except that the molar ratio of Si to Sn in the snts@sn is 2:1.
Example 7
This example provides a negative electrode material that is the same as example 1 except that the molar ratio of Si to Sn in the snts@sn is 18:1.
Example 8
This example provides a negative electrode material that is the same as example 1 except that the temperature of the hydrothermal treatment is 120 ℃.
Example 9
This example provides a negative electrode material that is the same as example 1 except that the temperature of the hydrothermal treatment is 230 ℃.
Example 10
This example provides a negative electrode material that is the same as example 1 except that the temperature is raised to 400 ℃ in a protective atmosphere and then the negative electrode material is kept warm.
Example 11
This example provides a negative electrode material that is the same as example 1 except that the temperature is raised to 1000 ℃ in a protective atmosphere and then the negative electrode material is kept warm.
Example 12
The comparative example provides a negative electrode material, which is the same as that of example 1 except that the existence form of Sn in SNTs@Sn is tin dioxide, namely, the temperature is kept for 1h after the temperature is raised to 800 ℃ at a heating rate of 2 ℃ min -1 in a protective atmosphere.
Comparative example 1
This comparative example provides a negative electrode material that is the same as example 1 except that the negative electrode material is SNTs.
N 2 isothermal adsorption and desorption tests are carried out on the anode materials in examples 1-12 and comparative example 1, the specific surface area and the pore volume of the anode materials obtained by the tests are shown in table 1, and isothermal adsorption and desorption curves of the anode materials in examples 1, 4 and 5 are shown in fig. 1;
Performing an X-ray diffraction test on the anode materials in examples 1, 4 and 5 by using an X-ray diffractometer, wherein the X-ray diagram is shown in figure 2;
carrying out X-ray energy spectrum test on the anode materials in the embodiments 1,4 and 5 by adopting an X-ray photoelectron spectrometer, wherein the X-ray energy spectrum obtained by the test is shown in figure 3;
The negative electrode materials in examples 1 to 12 and comparative example 1 were subjected to conductivity test in which the conductivity of the samples was measured using an FT 300L four-probe resistivity tester: rolling the material into blocks with the thickness of 100 mu m, testing to obtain a related resistance (R), obtaining the conductivity of the material according to a conductivity calculation formula, and testing to obtain the conductivity of the cathode material, wherein the conductivity is shown in a table 1;
The preparation of lithium ion batteries was performed by using the anode materials in examples 1 to 12 and comparative example 1, and the method for preparing lithium ion batteries was that the assembly of CR2032 type coin cells in this experiment was performed in a glove box (Mikarouna, shanghai) filled with argon, wherein the concentrations of H 2 O and O 2 were both less than 0.01 ppm. In the battery assembling process, the prepared active material is used as a negative electrode, and the electrolyte contains 1 mol L -1
A microporous polypropylene film (Celgard 2500, usa) was used as a separator and a metallic lithium sheet was used as a counter electrode, using a mixed organic solvent of ethylene carbonate to diethyl carbonate (volume ratio 1:1) of LiPF 6. After the battery is assembled, a sealing machine is used for compaction and encapsulation, and after standing for 24h, relevant electrochemical performance tests can be carried out; the lithium ion battery is subjected to initial discharge/charge specific capacity C test, wherein the initial discharge/charge specific capacity C test method is that the cycle performance of the relevant electrode materials is respectively researched under the current density of 100mA g -1, and the initial discharge/charge specific capacity C is obtained through test and is shown in a table 2; the prepared lithium ion battery was subjected to a cycle performance test, and the reversible capacity, coulombic efficiency and reversible lithium storage capacity after 300 charge and discharge cycles at a current density of 100mA/g are shown in table 2.
TABLE 1
TABLE 2
From tables 1 and 2 and fig. 1 to 3, it can be obtained that:
(1) The negative electrode material provided by the embodiments 1-5 has a higher specific surface area and a larger pore volume, and the lithium ion battery prepared from the negative electrode material has a higher initial discharge/charge specific capacity, and has a higher reversible capacity, coulombic efficiency and reversible lithium storage capacity after charge and discharge cycles;
As can be taken from fig. 1, the isothermal desorption curves of the anode materials in examples 1, 4 and 5 of the present invention conform to the combination of type i and type iv isotherms, with rapidly increasing adsorption at lower relative pressures (P/P 0 < 0.01) and hysteresis loops at higher relative pressures (0.4 < P/P 0 < 0.9) indicating the simultaneous presence of micropores and mesopores;
As can be seen from fig. 2, in examples 1,4 and 5, the anode materials all have diffraction peaks in the range of 20 to 30 o, and the wide diffraction peak of the anode material at 23.2 o in the XRD pattern indicates that the anode material is an amorphous material, and besides, no diffraction peak of Sn is detected, which means that Sn is highly dispersed in the snts@sn composite material; in addition, the XRD pattern can observe that the anode material increases to 15% with metal loading, and the peak intensity of the catalyst increases slightly due to the random array of three-dimensionally interconnected silica and tin, increasing the amount of heteroatoms in the parent material, possibly increasing the intensity of the characteristic broad peaks of the amorphous material;
as can be seen from fig. 3, the negative electrode materials loaded with different amounts of metallic tin show different characteristic peaks in the 3d region of Sn, wherein the two characteristic peaks at 487.4 and 495.8eV are attributed to the 3d5/2, 3d3/2 photoelectron vibration peaks in tetrahedrally coordinated Sn, while the characteristic peaks at 486.4 and 494.2eV are mainly attributed to the formation of SnO 2. The Sn species on the anode material of the X-ray energy spectrum specification mainly show tetrahedral coordination state and are successfully combined with SNTs;
As can be seen from table 2, in examples 1 to 5 of the present invention, the specific capacity of the negative electrode material after 300 charge and discharge cycles is continuously increased, and the coulomb efficiency is high, which results from the gradual activation of the SNTs on the one hand, and from the slow process required for the electrolyte to continuously permeate into the negative electrode material on the other hand;
(2) From a comparison of example 1 with examples 6 and 7, it is understood that the molar ratio of Si to Sn in SNTs@Sn in the present invention affects the performance of the negative electrode material; when the molar ratio of Si to Sn is lower, the specific surface area of SNTs@Sn is reduced, the electrochemical performance is reduced, and the conductivity is poor; when the molar ratio of Si to Sn is higher, the specific surface area of SNTs@Sn is increased, the pore volume is also changed, the improvement of the performance of the anode material is not facilitated, and the production cost of the anode material is increased due to the fact that the content of Sn is too high;
(3) As can be seen from a comparison of example 1 with examples 8 and 9, the temperature of the hydrothermal treatment of the present invention affects the performance of the anode material; when the temperature of the hydrothermal treatment is lower, the dissolution of reactants and the crystallization of products are affected, and the growth and the formation of an SNTs@Sn structure are not facilitated; when the temperature of the hydrothermal treatment is higher, the particle size of the metal Sn is increased, so that the electrochemical performance of the SNTs@Sn structure is affected;
(4) As is clear from comparison of example 1 with examples 10 and 11, the end temperature of the heat treatment increase in the present invention, i.e., the temperature of the heat preservation, affects the performance of the anode material; when the temperature of the heat preservation is low, sn exists in a SnO 2 state, which is not beneficial to improving the electrochemical performance of the anode material; when the temperature of the heat preservation is higher, sn is easy to sinter and agglomerate, blocks pore channels, is unfavorable for uniform loading of Sn, and is unfavorable for improving the electrochemical performance of the anode material;
(5) As is clear from the comparison of example 1 and example 12, the heat treatment in the reducing treatment in the preparation method of the anode material according to the present invention affects the performance of the anode material; when the heat treatment is omitted, that is, snO 2 in the anode material does not reduce metal Sn, the specific surface area of the anode material is increased, the pore volume is slightly reduced, the conductivity is weakened, the initial discharge/charge specific capacity 710, the reversible capacity 348, the coulomb efficiency 49.01% of the lithium ion battery prepared by the anode material, and the reversible lithium storage capacity 1713mah·g -1 are reduced, because the formation of SnO 2 increases the specific surface area, the pore volume is reduced, the mass transfer rate is reduced, and the conductivity is reduced;
(6) As can be seen from the comparison between the embodiment 1 and the comparative example 1, the invention provides the negative electrode material comprising SNTs@Sn, wherein the SNTs@Sn is prepared by modifying the silicon nanotube by adopting metal Sn, so that the conductivity of the lithium ion battery prepared by the negative electrode material is improved, the ion diffusion path of the lithium ion battery is shortened, the initial discharge/charge specific capacity of the lithium ion battery is improved, and the volume expansion rate of the lithium ion battery is reduced, so that the lithium ion battery has higher cycling stability.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The negative electrode material is characterized by comprising SNTs@Sn, wherein Sn in the SNTs@Sn is coated on the inner wall and the outer wall of the SNTs.
2. The anode material according to claim 1, wherein Sn in the snts@sn exists in a tetrahedral coordination configuration.
3. The negative electrode material according to claim 1, wherein the molar ratio of Si to Sn in SNTs@Sn is (5-15): 1.
4. A method for producing the anode material according to any one of claims 1 to 3, characterized by comprising:
and synthesizing a precursor on the surface of the template by adopting an in-situ synthesis method, removing the template, and then carrying out reduction treatment to obtain SNTs@Sn.
5. The method of claim 4, wherein the template is a nickel hydrazine complex template.
6. The method of claim 4, wherein the in situ synthesis comprises hydrolyzing an organosilicon compound and a water-soluble tin salt on the surface of the template;
the hydrolysis organosilicon compound is any one or the combination of at least two of tetraethyl silicate, tetraethoxysilane and methyl silicate;
the water-soluble tin salt is any one or a combination of at least two of tin tetrachloride, tin tetrachloride pentahydrate or stannous chloride.
7. The method of preparing according to claim 4, wherein removing the template comprises treating with an acid;
the acid adopted in the acid treatment is hydrochloric acid with the concentration of 0.5-1.5 mol/L;
The acid treatment time is 5-7 days.
8. The method according to claim 4, wherein the reduction treatment comprises a hydrothermal treatment followed by a heat treatment in a protective atmosphere;
The temperature of the hydrothermal treatment is 150-190 ℃ and the time is 4-8 hours;
the heat treatment comprises heating and heat preservation which are sequentially carried out;
The temperature rising rate is 1-5 ℃ and min -1, and the end point temperature is 600-800 ℃;
The heat preservation time is 1-3 h.
9. The preparation method according to claim 4, characterized in that the preparation method comprises:
Hydrolyzing the surface of the Ni-N 2H4 nano rod to synthesize a precursor, performing acid treatment by adopting hydrochloric acid to remove a template, performing hydrothermal treatment at 150-190 ℃ for 4-8 hours, heating to 600-800 ℃ in a protective atmosphere at the heating rate of 1-5 ℃ min -1, and then preserving heat for 1-3 hours to obtain SNTs@Sn.
10. A battery comprising a negative electrode sheet prepared from the negative electrode material according to any one of claims 1 to 3, or a negative electrode sheet prepared from the negative electrode material prepared by the method according to any one of claims 4 to 9.
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