CN113707855B - Lithium ion battery negative electrode composite material and preparation method thereof - Google Patents
Lithium ion battery negative electrode composite material and preparation method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title abstract description 12
- 229910007717 ZnSnO Inorganic materials 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 14
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000002733 tin-carbon composite material Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000007773 negative electrode material Substances 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000011366 tin-based material Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 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
-
- 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
- H01M4/387—Tin or alloys based on tin
-
- 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
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of lithium ion batteries, and discloses a lithium ion battery negative electrode composite material and a preparation method thereof. By ZnSnO 3 The micro-box is a precursor, and SnO is synthesized in situ in the precursor through hydrothermal reaction 2 And (3) the ZIF-8 micro-box is subjected to calcination pyrolysis to reduce the material into the MB/TC composite material with the nitrogen-doped carbon skeleton coated with the Sn nano particles, and the MB/TC composite material is used as a negative electrode material. The invention is expected to lead the lithium ion battery to have high specific capacity with extremely high stability, and is a successful strategy for improving the electrochemical performance of the lithium ion battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a lithium ion battery negative electrode composite material and a preparation method thereof. In particular to a nitrogen-doped tin-carbon composite material (MB/TC) with a lithium ion battery cathode hollow micro-box structure and a preparation method thereof.
Background
The current social energy demand is larger and larger, and the energy proportion in production and life is gradually increased. Along with the development of industry, the use amount of traditional energy sources is also increased sharply, and the use cost is also increased obviously. Therefore, the development of new energy is urgent, and the chemical power supply is highlighted in the new energy field due to the advantages of good cycle performance, high energy density, good operability and the like. Under the condition that the updating speed of the portable electronic products is extremely high and electric automobiles are greatly developed, the advantages of the lithium ion battery gradually become important attention objects of researchers, and therefore the lithium ion battery always stands at the beginning of a chemical power supply. The negative electrode material of the lithium ion battery contacted by the current method is mainly graphite, but the specific capacity of the graphite is low, and the energy requirement cannot be met, so that the application of the lithium ion battery in some high-power equipment is greatly limited.
The tin-based material is a cathode material with great development prospect at present due to the advantages of abundant reserves, environmental protection, no toxicity, low cost and the like, and has great research and application development values. The lithium storage mechanism of the tin-based material accords with an alloy material, namely 4.4 Li are combined in the process of forming the alloy + This makes its theoretical specific capacity much higher than that of graphite by a factor of 2. And the intercalation/deintercalation potential of tin is far higher than the precipitation potential of lithium, so that the problem of short circuit caused by the generation of lithium dendrite in the charge and discharge process is solved, and higher safety performance is shown.
Tin-based materials, while having considerable advantages over graphite, suffer from certain drawbacks. That is, the material generates larger stress, namely volume expansion effect, in the process of lithium intercalation/deintercalation. This can make it difficult to maintain the integrity of the material, ultimately destroying the lithium storage space. Meanwhile, the characteristics of soft and easy agglomeration, low melting point and the like of the tin-based material bring a plurality of challenges to the preparation and research of the tin-based negative electrode material.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a lithium ion battery negative electrode composite material and a preparation method thereof, in particular to a nitrogen-doped tin-carbon composite material (MB/TC) with a lithium ion battery negative electrode hollow micro-box structure and a preparation method thereof. By ZnSnO 3 The micro-box is a precursor, and SnO is synthesized in situ in the precursor through hydrothermal reaction 2 And (3) the ZIF-8 micro-box is subjected to calcination pyrolysis to reduce the material into the MB/TC composite material with the nitrogen-doped carbon skeleton coated with the Sn nano particles, and the MB/TC composite material is used as a negative electrode material. The invention is expected to lead the lithium ion battery to have high specific capacity with extremely high stability, and is a successful strategy for improving the electrochemical performance of the lithium ion battery.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a lithium ion battery negative electrode composite material; znCl 2 And C 6 H 5 Na 3 O 7 ·2H 2 O is stirred and dissolved in deionized water, and SnCl which is completely dissolved is dissolved 4 Adding ethanol solution into the above solution, adding NaOH aqueous solution into the mixed solution, and reacting for 20-40min. The precursor ZnSn (OH) can be obtained by the solution reaction 6 . In the precursor ZnSn (OH) 6 Adding 20-40mL NaOH solution, and forming ZnSn (OH) with hollow microcube structure by alkali etching 6 The suspension was then centrifugally dried overnight, and the dried white powder was taken out and put into a tube furnace for dehydration calcination. Naturally cooling to obtain ZnSnO 3 A micro-box.
Dissolving 2-methylimidazole in 20-30mL of solution prepared by mixing DMF and deionized water, and adding ZnSnO 3 The micro-box is treated by ultrasonic for 20-40min, and the solution is put into a 50mL reaction kettle for hydrothermal reaction. After the reaction is stopped, the solution in the kettle is taken out and treated to obtain the SnO composition 2 Powder of ZIF-8 micro-box, snO 2 And (3) decomposing and carbonizing the ZIF-8 micro-box, and cooling the material to obtain the nitrogen-doped tin-carbon composite material (MB/TC) with the hollow micro-box structure.
The preparation method of the lithium ion battery negative electrode composite material comprises the steps of; the method comprises the following specific steps:
(1)ZnSn(OH) 6 is prepared from the following steps:
a. first, a solution A is prepared: 0.270 to 0.280g of ZnCl 2 And 0.580 to 0.590gC 6 H 5 Na 3 O 7 ·2H 2 O is dissolved in deionized water (10-30 ml); solution B was then prepared: to dissolve SnCl completely 4 Adding ethanol solution (0.1-0.3 mol/L5-15 mL) into A to obtain solution B;
b. aqueous NaOH solution 0.3-0.5 mol/L40-60 mL) was added to the B solution and reacted for 20-40min. ZnSn (OH) can be obtained by the above solution reaction 6 ；
(2)ZnSnO 3 Preparation of the micro-box:
a. in (1) ZnSn (OH) 6 Adding 20-40 mM LNaOH solution (1-3 mol/L), and drippingStirring for 10-20min after completion, and forming hollow ZnSn (OH) by alkali etching 6 A microcube structure;
b, centrifuging the suspension and drying the suspension in a drying oven overnight;
c. taking out the dried white powder, putting the white powder into a tube furnace for dehydration and calcination, and naturally cooling to obtain ZnSnO 3 A micro-box;
(3) Preparation of tin-carbon material MB/TC:
a. dissolving 170-190mg of 2-methylimidazole in 20-30mL of a solution prepared by mixing DMF and deionized water;
b. adding 170-190mg ZnSnO 3 Carrying out ultrasonic treatment on the micro-box for 20-40min, and carrying out hydrothermal reaction on the solution to 50 mL;
c. after the reaction is stopped, the solution is taken out and treated to obtain the SnO composition 2 Powder of ZIF-8 micro-box;
d. SnO is prepared 2 And (3) decomposing and carbonizing the ZIF-8 micro-box at 700-900 ℃ in an argon atmosphere for 1-3 hours, and cooling the material to obtain the nitrogen-doped tin-carbon composite material (MB/TC) with the hollow micro-box structure.
Further, the ZnSnO 3 The preparation of the micro-box adopts a coprecipitation method to prepare materials.
Further, the step (2) is ZnSnO 3 The calcining condition temperature in the tube furnace in the preparation of the micro-box is 400-500 ℃, and the temperature rising speed is as follows: 0.5-2 ℃/min, and preserving heat for 1-3h.
Further, in the step (3), the volume ratio of DMF to deionized water is 2:1-4:1.
Further, the hydrothermal reaction conditions in the step (3) are as follows: reaction temperature: 140-150 ℃; heating rate: 2-4 ℃/min; reaction time: 36-72h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The material prepared by the invention has a unique hollow micro-box structure, and provides a buffer space to solve the volume expansion of the material in the charge and discharge process.
(2) The inter-connected pores in the material provide effective and rapid channels for Li+ diffusion, and the nitrogen-doped carbon matrix enhances the structural stability while ensuring rapid electron transfer.
(3) The strong coupling of the nano Sn particles and the hollow carbon micro-box skeleton can effectively inhibit the mechanical strain in the lithium intercalation/deintercalation process and shorten Li + The single Sn nano-particles are encapsulated in the carbon micro-box, so that the Sn nano-particles can be effectively prevented from agglomerating and being directly exposed to electrolyte in the charge-discharge process.
(4) The MB/TC composite material is used as a negative electrode material, the electrochemical performance of the lithium ion battery is excellent, and the battery can keep high specific capacity with extremely high stability no matter the battery is circulated under a small current density or different current densities.
Drawings
FIG. 1 is an X-ray diffraction pattern of a nitrogen-doped tin-carbon composite (MB/TC) according to example 1 of the present invention.
FIG. 2 is a graph showing the cycle performance of the nitrogen-doped tin-carbon composite (MB/TC) of example 1 of the present invention as a negative electrode for a lithium ion battery.
Fig. 3 is a graph showing the long cycle performance of the nitrogen-doped tin-carbon composite (MB/TC) of example 1 of the present invention as a negative electrode of a lithium ion battery.
Detailed Description
The present invention is described in detail below by way of specific examples, but the scope of the present invention is not limited thereto. Unless otherwise specified, the experimental methods used in the present invention are all conventional methods, and all experimental equipment, materials, reagents, etc. used can be obtained from commercial sources.
Example 1
A nitrogen-doped tin-carbon composite material (MB/TC) with a lithium ion battery cathode hollow micro-box structure and a preparation method thereof specifically comprise the following steps:
(1)ZnSn(OH) 6 is prepared from the following steps:
0.273g ZnCl under stirring 2 And 0.588g C 6 H 5 Na 3 O 7 2H2O was dissolved in deionized water (20 ml) and then the dissolved SnCl was complete 4 Ethanol solution (0.2 mol/L10 mL) of the above-mentioned solution, and NaOH aqueous solution(0.4 mol/L50 mL) was added to the mixed solution and reacted for 30min. The precursor ZnSn (OH) can be obtained by the solution reaction 6 。
(2)ZnSnO 3 Preparation of the micro-box:
in the precursor ZnSn (OH) 6 30mL of NaOH solution (2 mol/L) was added and stirred for 15min to form hollow ZnSn (OH) by alkali etching 6 The microcubes were then dried by centrifugation overnight and the dried white powder was removed and placed in a tube furnace for dehydration calcination. Naturally cooling to obtain ZnSnO 3 A micro-box.
(3) Preparation of tin-carbon material MB/TC:
180mg of 2-methylimidazole is dissolved in 24mL of a solution prepared by mixing DMF and deionized water, and 180mg of ZnSnO is added 3 The micro-box is treated by ultrasonic for 30min, and the solution is put into a 50mL reaction kettle for hydrothermal reaction. After the reaction is stopped, the solution in the kettle is taken out and treated to obtain the SnO composition 2 Powder of ZIF-8 micro-box, snO 2 And decomposing and carbonizing the ZIF-8 micro-box, and cooling the material to obtain the nitrogen-doped tin-carbon composite material (MB/TC) with the hollow micro-box structure.
As can be seen from the ray diffraction pattern of FIG. 1X, all peaks in the XRD pattern of MB/TC can correspond well to the tin crystal structure (JCPLS card No. 04-0673), further confirming the successful growth of metallic Sn.
The excellent cycle performance of MB/TC is demonstrated by the cycle performance chart of FIG. 2MB/TC at 100mA g-1.
By FIG. 3MB/TC at 2A g -1 Long term cycling diagrams at current densities of (2) indicate the cycling stability of MB/TC at higher current densities.
Example 2
A nitrogen-doped tin-carbon composite material (MB/TC) with a lithium ion battery cathode hollow micro-box structure and a preparation method thereof specifically comprise the following steps:
(1) Precursor ZnSn (OH) 6 Is prepared from the following steps:
0.280g ZnCl is stirred 2 And 0.600g C 6 H 5 Na 3 O 7 2H2O was dissolved in deionized water (30 ml),then dissolve the SnCl completely 4 To the above solution was added an ethanol solution (0.2 mol/L20 mL), and an aqueous solution of NaOH (0.4 mol/L60 mL) was added to the mixed solution, and reacted for 40 minutes. The precursor ZnSn (OH) can be obtained by the solution reaction 6 。
(2)ZnSnO 3 Preparation of the micro-box:
in the precursor ZnSn (OH) 6 40mL of NaOH solution (2 mol/L) was added and stirred for 20min to form hollow ZnSn (OH) by alkali etching 6 The microcubes were then dried by centrifugation overnight and the dried white powder was removed and placed in a tube furnace for dehydration calcination. Naturally cooling to obtain ZnSnO 3 A micro-box.
(3) Preparation of tin-carbon material MB/TC:
190mg of 2-methylimidazole was dissolved in 30mL of a solution of DMF and deionized water, and 190mg of ZnSnO was added 3 The micro-box is treated by ultrasonic for 40min, and the solution is put into a 60mL reaction kettle for hydrothermal reaction. After the reaction is stopped, the solution in the kettle is taken out and treated to obtain the SnO composition 2 Powder of ZIF-8 micro-box, snO 2 And decomposing and carbonizing the ZIF-8 micro-box, and cooling the material to obtain the nitrogen-doped tin-carbon composite material (MB/TC) with the hollow micro-box structure.
Example 3
A nitrogen-doped tin-carbon composite material (MB/TC) with a lithium ion battery cathode hollow micro-box structure and a preparation method thereof specifically comprise the following steps:
(1) Precursor ZnSn (OH) 6 Is prepared from the following steps:
0.270g ZnCl is stirred 2 And 0.580g C 6 H 5 Na 3 O 7 2H2O was dissolved in deionized water (10 ml) and then the dissolved SnCl was complete 4 To the above solution was added an ethanol solution (0.2 mol/L5 mL), and an aqueous solution of NaOH (0.4 mol/L40 mL) was added to the mixed solution, and reacted for 20 minutes. The precursor ZnSn (OH) can be obtained by the solution reaction 6 。
(2)ZnSnO 3 Preparation of the micro-box:
in the precursor ZnSn (OH) 6 30mL NaOH was addedThe solution (2 mol/L) was stirred for 10min and hollow ZnSn (OH) was formed by alkali etching 6 The microcubes were then dried by centrifugation overnight and the dried white powder was removed and placed in a tube furnace for dehydration calcination. Naturally cooling to obtain ZnSnO 3 A micro-box.
(3) Preparation of tin-carbon material MB/TC:
170mg of 2-methylimidazole is dissolved in 20mL of a solution prepared by mixing DMF and deionized water, and 170mg of ZnSnO is added 3 The micro-box is treated by ultrasonic for 20min, and the solution is put into a 40mL reaction kettle for hydrothermal reaction. After the reaction is stopped, the solution in the kettle is taken out and treated to obtain the SnO composition 2 Powder of ZIF-8 micro-box, snO 2 And decomposing and carbonizing the ZIF-8 micro-box, and cooling the material to obtain the nitrogen-doped tin-carbon composite material (MB/TC) with the hollow micro-box structure.
The above-described embodiments are only preferred embodiments of the invention, and not all embodiments of the invention are possible. Any obvious modifications thereof, which would be apparent to those skilled in the art without departing from the principles and spirit of the present invention, should be considered to be included within the scope of the appended claims.
Claims (5)
1. A preparation method of a nitrogen-doped tin-carbon composite material with a lithium ion battery cathode hollow micro-box structure is characterized by comprising the following specific steps:
(1)ZnSn(OH) 6 is prepared from the following steps:
a. first, a solution A is prepared: 0.270 to 0.280g of ZnCl 2 And 0.580 to 0.590gC 6 H 5 Na 3 O 7 ·2H 2 O is dissolved in 10-30ml deionized water; solution B was then prepared: dissolving completely 0.1-0.3 mol/L5-15 mLSnCl 4 Adding the ethanol solution of (a) into the solution A to obtain a solution B;
b. adding 0.3-0.5mol/L of 40-60mL of aqueous solution of NaOH into the solution B, and reacting for 20-40min; znSn (OH) is obtained by reacting the above solutions 6 ；
(2)ZnSnO 3 Preparation of the micro-box:
a. at the position of（1）ZnSn(OH) 6 Adding 20-40mL of 1-3mol/L NaOH solution, stirring for 10-20min after dripping, and performing alkali etching to form hollow ZnSn (OH) 6 A microcube structure;
b, centrifuging the suspension and drying the suspension in a drying oven overnight;
c. taking out the dried white powder, putting the white powder into a tube furnace for dehydration and calcination, and naturally cooling to obtain ZnSnO 3 A micro-box;
(3) Preparation of tin-carbon material MB/TC:
a. dissolving 170-190mg of 2-methylimidazole in 20-30mL of a solution prepared by mixing DMF and deionized water;
b. adding 170-190mg ZnSnO 3 Carrying out ultrasonic treatment on the micro-box for 20-40min, and carrying out hydrothermal reaction on the solution to 50 mL;
c. after the reaction is stopped, the solution is taken out and treated to obtain the SnO composition 2 Powder of ZIF-8 micro-box;
d. SnO is prepared 2 And (3) decomposing and carbonizing the ZIF-8 micro-box at 700-900 ℃ in an argon atmosphere for 1-3 hours, and cooling the material to obtain the nitrogen-doped tin-carbon composite material with the hollow micro-box structure.
2. The method for preparing the nitrogen-doped tin-carbon composite material with the lithium ion battery negative electrode hollow micro-box structure as claimed in claim 1, wherein the ZnSnO is prepared by the following steps of 3 The preparation of the micro-box adopts a coprecipitation method to prepare materials.
3. The method for preparing the nitrogen-doped tin-carbon composite material with the lithium ion battery negative electrode hollow micro-box structure according to claim 2, wherein the step (2) is ZnSnO 3 The calcining condition temperature in the tube furnace in the preparation of the micro-box is 400-500 ℃, and the temperature rising speed is as follows: 0.5-2 ℃/min, and preserving heat for 1-3h.
4. The method for preparing the nitrogen-doped tin-carbon composite material with the lithium ion battery negative electrode hollow micro-box structure according to claim 3, wherein the volume ratio of DMF to deionized water in the step (3) is 2:1-4:1.
5. The method for preparing the nitrogen-doped tin-carbon composite material with the lithium ion battery negative electrode hollow micro-box structure according to claim 4, wherein the hydrothermal reaction condition in the step (3) is as follows: reaction temperature: 140-150 ℃; heating rate: 2-4 ℃/min; reaction time: 36-72h.
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