CN114105760B - Nanometer flaky tin oxalate high-performance lithium and sodium storage material and battery - Google Patents

Nanometer flaky tin oxalate high-performance lithium and sodium storage material and battery Download PDF

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CN114105760B
CN114105760B CN202111177998.9A CN202111177998A CN114105760B CN 114105760 B CN114105760 B CN 114105760B CN 202111177998 A CN202111177998 A CN 202111177998A CN 114105760 B CN114105760 B CN 114105760B
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oxalate
tin
tin oxalate
storage material
sodium
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CN114105760A (en
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赵世强
李广辉
王舜
金辉乐
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Wenzhou University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/02—Dicarboxylic acids
    • C07C55/06—Oxalic acid
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
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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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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the technical field of electrode materials, and particularly relates to a nano flaky tin oxalate high-performance lithium and sodium storage material and a battery. The preparation method of the nano flaky tin oxalate high-performance lithium and sodium storage material comprises the following steps: s1, respectively dissolving oxalic acid or oxalate and tin salt to obtain oxalic acid or oxalate solution and tin salt solution, and then dropwise adding the oxalic acid or oxalate solution into the tin salt solution under stirring at a certain rate to obtain tin oxalate micrometer hollow tubes; s2, adding the tin oxalate micron hollow tubes obtained in the step S1 into the dispersion liquid, uniformly mixing, crushing, centrifuging, washing and drying to obtain the nano flaky tin oxalate high-performance lithium and sodium storage material. According to the invention, the tin salt and the oxalate are used as main materials to prepare the tin oxalate micron hollow tube, and then the tin oxalate micron hollow tube is crushed by the ball mill to obtain the tin oxalate nano-sheet, so that the source of raw materials is wide, the cost is low, the raw materials are easy to obtain, and meanwhile, the preparation process is simpler, and the problem of larger synthesis size of the tin oxalate is effectively solved.

Description

Nanometer flaky tin oxalate high-performance lithium and sodium storage material and battery
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a nano flaky tin oxalate high-performance lithium and sodium storage material and a battery.
Background
As energy is continuously consumed, secondary batteries have received attention from many researchers. Lithium ion batteries have been used in a large scale, such as portable electronic products, electric vehicles, and electric energy storage; sodium ion batteries, although not commercially available on a large scale, have attracted attention from many researchers.
In lithium ion batteries, the current commercial negative electrode material is graphite, but due to its low lithium storage capacity (372 mAh g -1) it is difficult to meet the increasing demands. For a long time, researchers have been working to find new anode materials. In sodium ion batteries, the negative electrode is also of great interest as one of the important components. Tin oxalate is used as a tin-based material, has the advantages of simple synthesis, low working voltage and the like, and is paid attention to by a plurality of scientific researchers. We summarize the literature, patents on tin oxalate synthesis, respectively.
1. (Current APPLIED PHYSICS 2014, 14, 892-896), immersing tin in an alcohol-based oxalic acid solution, displacing Sn 2+ from H +, and then immediately reacting Sn 2+ with C 2O4 2- to produce SnC 2O4 micro rods.
2. (Ceramics International,2018, 44, 13495-13501), dissolving tin dichloride in 20mL of distilled water, dissolving dimethyl oxalate and lithium acetate in 30mL of a mixed solution of distilled water and ethylene glycol (1:1), transferring into a polytetrafluoroethylene reaction kettle, and reacting for 30 minutes at 180 ℃ to obtain tin oxalate, wherein the reaction is complex and is not suitable for batch production.
3. (MATERIALS SCIENCE IN Semiconductor Processing,2016, 56, 83-89), sodium oxalate was dissolved in distilled water, followed by dropwise addition of an aqueous solution of tin dichloride in a water bath at 70℃to obtain tin oxalate micro-blocks of 50 μm in length and 30 μm in width.
4. (J Mater Sci,2020, 55, 11524-11534), anhydrous oxalic acid was dispersed in 60mL of polyethylene glycol (400-poly-ethylene-glycol) and mixed uniformly with magnetic stirring, then tin dichloride was added to 3mL of ethylene glycol and added to a polyethylene glycol solution of anhydrous oxalic acid, 5mL of anhydrous ethanol was poured and stirred for 20 minutes, 5mL of ultrapure water was further added, stirring was continued at room temperature for 2 hours, and tin oxalate nanowires were obtained by centrifugation.
5. (J Electroceram,2006, 17, 895-898), dropwise adding 0.5M aqueous solution of oxalic acid (ethanol solution) to 0.5M aqueous solution of tin dichloride (ethanol solution) or reversely dropwise adding under constant temperature conditions (30, 50, 60, 70, 80, 90 ℃) to generate tin oxalate, wherein the 30 ℃ generated micron-sized tin oxalate and the 70 ℃ generated micron-sized flocculent tin oxalate are larger.
6. (Nano-Micro Lett, 2011,3 (1), 34-42) under magnetic stirring, sequentially dissolving 1mmol oxalic acid and 1mmol tin dichloride in 15mL tetrahydrofuran, then dropwise adding 6mL deionized water, and continuously stirring for 5 minutes to obtain fiber tin oxalate with the diameter of 200-300 nm and the length of tens of micrometers.
7. (Ionics, 2014, 20, 841-848) 30mL of oxalic acid solution (the solvent is a mixed solution of ultrapure water and ethylene glycol, the ratio is 1:2) is poured into 30mL of tin dichloride solution (the solvent and oxalic acid), and the solution is reacted for 3 hours under magnetic stirring at 25 ℃ to obtain tin oxalate micron rods with the size of 1.2+/-0.3 μm wide and 10+/-3.4 μm long.
8. (ACS appl. Mater. Interfaces2017, 9, 25941-25951), 0.001M tin chloride and 0.001M sodium oxalate were dissolved in 9mL distilled water and 16mL ethylene glycol, and transferred to a polytetrafluoroethylene reaction vessel to react at 140℃for 12 hours, to obtain irregularly shaped tin oxalate.
In the patent, a carbon nano tube doped tin oxalate is taken as a negative electrode material (Yao Yaochun, wei Runhong and the like, a preparation method of the carbon nano tube doped tubular tin oxalate negative electrode material, chinese patent application number: 202010985058.1) describes that an oxalic acid solution and an SnSO 4 solution are respectively added into a carbon nano tube solution in a high-speed shearing machine, stirring, standing, centrifugal filtering, washing and drying are carried out, and the carbon nano tube doped tubular tin oxalate negative electrode material is obtained, wherein the tubular tin oxalate is 2-5 mu m wide and 10-15 mu m long, has larger size, even if the carbon nano tube with good conductivity is doped, the cycle performance is about 100 circles, only has the reversible capacity of 650mAh g -1, the multiplying power performance is poor, and the carbon nano tube doped tubular tin oxalate negative electrode material is not used as a negative electrode of a sodium ion battery for testing. In another patent, a tin oxalate and graphene co-doped tin dioxide negative electrode material (Yao Yaochun, wei Runhong, etc., a preparation method of the tin oxalate and graphene co-doped tin dioxide negative electrode material, china patent application No. 202010985061.3) describes that an oxalate solution, graphene and a tin salt solution are fully mixed and reacted to obtain a black suspension, and sintering is carried out at 250-350 ℃ to obtain a SnO 2/SnC2O4/RGO composite material, wherein the obtained product is a mixture of tin dioxide and tin oxalate and is not pure SnC 2O4/RGO, and the reversible capacity of 680mAh g -1 is only after 100 circles of the composite material is circulated.
In summary, in these documents and patents, there are many mixed solutions as solvents, which are inconvenient to prepare, and the hydrothermal reaction or solvothermal reaction has a long preparation period, and the hollow micron hollow tube structure is not appeared, and most of the solutions are solid tubes or solid particles, so that the synthesis is complicated, the particles are larger, and the particle size is large, which is a key factor for limiting the performance of the material battery.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provides a nano flaky tin oxalate high-performance lithium and sodium storage material and a battery.
The technical scheme adopted by the invention is as follows: the preparation method of the nano flaky tin oxalate high-performance lithium and sodium storage material comprises the following steps:
s1, respectively dissolving oxalic acid or oxalate and tin salt to obtain oxalic acid or oxalate solution and tin salt solution, and then dropwise adding the oxalic acid or oxalate solution into the tin salt solution under stirring at a certain rate to obtain tin oxalate micrometer hollow tubes;
s2, adding the tin oxalate micron hollow tubes obtained in the step S1 into the dispersion liquid, uniformly mixing, crushing, centrifuging, washing and drying to obtain the nano flaky tin oxalate high-performance lithium and sodium storage material.
As a further technical scheme, the oxalate is sodium oxalate or potassium oxalate.
As a further technical scheme, the tin salt is tin dichloride or stannous sulfate.
As a further technical scheme, the solvent in the oxalic acid or oxalate solution and the tin salt solution is one or more of ethanol, glycerol, ethylene glycol and dimethylformamide.
As a further technical scheme, in the step S1, the molar ratio of tin dichloride to oxalic acid is 1: 1-2.
As a further technical scheme, the tin oxalate micron hollow tubes of step S2 are crushed by ball milling, and the dispersion liquid used is one or more of ultrapure water, ethanol and ethylene glycol.
As a further technical scheme, when tin oxalate is ball-milled, the rotating speed of the ball mill is 920-1200r/min, and the ball milling time of the ball mill is 2-6 h.
The invention further provides a battery assembled by the nano flaky tin oxalate high-performance lithium and sodium storage material, and the nano flaky tin oxalate high-performance lithium and sodium storage material is used as a negative electrode material.
As a further technical scheme, the battery is a lithium ion battery or a sodium ion battery.
As a further technical scheme, the preparation method comprises the following steps:
(A) Weighing a nano flaky tin oxalate high-performance lithium and sodium storage material, acetylene black and sodium alginate, adding a proper amount of distilled water, uniformly mixing, grinding and stirring to form paste, and coating the paste on a copper foil;
(B) And drying, slicing, assembling and tabletting the copper foil coated with the tin oxalate negative electrode material to obtain the lithium ion battery or the sodium ion battery.
The beneficial effects of the invention are as follows: according to the invention, the tin salt and the oxalate are used as main materials to prepare the tin oxalate micron hollow tube, and then the tin oxalate micron hollow tube is crushed by the ball mill to obtain the tin oxalate nano-sheet, so that the source of raw materials is wide, the cost is low, the raw materials are easy to obtain, and meanwhile, the preparation process is simpler, and the problem of larger synthesis size of the tin oxalate is effectively solved. In the invention, tin oxalate nanosheets are used as negative electrode materials of lithium ion batteries and sodium ion batteries. In some embodiments of the present invention, in a lithium ion battery, compared with graphite as the negative electrode, the specific capacity of 372mAh g -1 is improved greatly, and the battery capacity of 50 charging and discharging cycles is stabilized at 982mAh g -1 under the current density of 100mA g -1; in a sodium ion battery, the tin oxalate nanosheets have stable capacity of 355mAh g -1 after being charged and discharged for 50 circles under the current density of 50mA g -1, and have good circulation stability. The tin oxalate nanosheets provided by the invention are suitable for popularization and application as negative electrode materials of lithium ion batteries and sodium ion batteries.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a Scanning Electron Microscope (SEM) image and a Transmission Electron Microscope (TEM) image of a tin oxalate hollow-tube lithium and sodium storage material prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image and a Transmission Electron Microscope (TEM) image of the lithium and sodium storage material of tin oxalate nanoplatelets prepared in example 1 of the present invention;
FIG. 3 is an X-ray diffraction chart of a tin oxalate hollow micron hollow tube and a tin oxalate nanosheet lithium and sodium storage material prepared in example 1 of the present invention;
FIG. 4 is a graph showing the test of the cycling stability of the tin oxalate hollow micron hollow tube and the tin oxalate nanosheet lithium and sodium storage material prepared in example 1 of the present invention at a current density of 100mA g -1;
FIG. 5 is a graph showing the test of the cycling stability of the tin oxalate hollow micron hollow tube and the tin oxalate nanosheet lithium and sodium storage material prepared in example 1 of the present invention at a current density of 1000mA g -1;
FIG. 6 is a graph showing the rate cycle performance of the tin oxalate hollow micron hollow tube and the tin oxalate nanosheet lithium and sodium storage material prepared in example 1 of the present invention under different current densities;
FIG. 7 is a graph showing the test of the cycling stability of the tin oxalate nanoplatelets lithium and sodium storage material prepared in example 1 of the present invention at a current density of 50mA g -1.
FIG. 8 is a graph for testing the cycle stability of the tin oxalate nanosheet lithium and sodium storage material prepared in example 2 of the present invention at a current density of 1000mA g -1;
FIG. 9 is a graph showing the test of the cycling stability of the tin oxalate nanosheet lithium and sodium storage material prepared in example 3 of the present invention at a current density of 1000mA g -1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
The invention provides a nano flaky tin oxalate high-performance lithium and sodium storage material, and the preparation method comprises the following steps:
S1, respectively adding a certain amount of tin salt and oxalate into two beakers filled with solvents, carrying out ultrasonic dissolution to obtain a reaction solution, then dropwise adding the oxalate solution into the tin salt solution at a certain speed, and stirring the magnetons at a certain rotating speed to obtain a tin oxalate micron hollow tube;
s2, adding the tin oxalate micron hollow tubes obtained in the step S1 into the dispersion liquid, uniformly mixing, putting into a ball milling tank, crushing by using a ball mill according to a certain rotating speed, taking out, centrifuging, washing and drying to obtain graphene nano sheets, and using the graphene nano sheets as anode materials of lithium ion batteries and sodium ion batteries.
In some embodiments of the present invention, the tin salt used in step S1 is tin dichloride, stannous sulfate, or the like.
In some embodiments of the present invention, the oxalate used in step S1 is sodium oxalate, potassium oxalate, or the like
In some embodiments of the present invention, the solvent used in step S1 is ethanol, glycerol, ethylene glycol, dimethylformamide, or the like.
In some embodiments of the present invention, the dropping rate is 0.75 to 1mL/min.
In some embodiments of the invention, the molar ratio of tin dichloride to oxalic acid in step S1 is 1: 1-2.
In some embodiments of the present invention, the stirring rate of the magnet in step S1 is 400-550 r/min.
In some embodiments of the present invention, the dispersion used in the tin oxalate ball milling of step S2 is ultrapure water, ethanol, ethylene glycol, or the like.
In some embodiments of the invention, the rotation speed of the ball mill is 920-1200r/min when the tin oxalate ball mill in the step S2 is used.
In some embodiments of the present invention, during the tin oxalate ball milling in the step S2, the ball milling time of the ball mill is 2-6 hours.
In some embodiments of the present invention, the size of the tin oxalate micro hollow tube synthesized in step S1 is 2-3 μm.
In some embodiments of the invention, the size of the tin oxalate nanoplatelets after ball milling in step S2 is 100-600nm.
The invention also provides a lithium ion battery and a sodium ion battery assembled by the tin oxalate nanosheet anode material, and the preparation method comprises the following steps:
(A) Weighing tin oxalate nanosheet anode material, acetylene black and sodium alginate, adding a proper amount of distilled water, uniformly mixing, grinding and stirring to form paste, and coating the paste on a copper foil;
(B) And drying, slicing, assembling and tabletting the copper foil coated with the tin oxalate negative electrode material to obtain the lithium ion battery and the sodium ion battery.
The following are some embodiments of the invention.
Example 1:
S1, respectively adding 1.2g of tin dichloride and 0.45g of oxalic acid into two beakers filled with 20mL of ethanol, performing ultrasonic dissolution to obtain a reaction solution, then dropwise adding the oxalic acid solution into the ethanol solution of the tin dichloride at a rate of 1mL/min, and stirring the magnetic particles at a rotating speed of 500r/min to obtain tin oxalate micro hollow tubes;
S2, adding the tin oxalate hollow micron hollow tube obtained in the step S1 into the ultra-pure water dispersion, uniformly mixing, putting into a ball milling tank, crushing by using a ball mill at the rotating speed of 920r/min, taking out, centrifuging, washing and drying to obtain the graphene nano sheet for lithium and sodium storage materials.
Example 2:
S1, respectively adding 1.2g of tin sulfate and 0.90g of sodium oxalate into two beakers filled with 20mL of glycerol, performing ultrasonic dissolution to obtain a reaction solution, then dropwise adding the oxalic acid solution into the ethanol solution of tin dichloride at a rate of 0.8mL/min, and stirring the magnetic particles at a rotating speed of 450r/min to obtain tin oxalate micron hollow tubes;
s2, adding the tin oxalate hollow micron hollow tube obtained in the step S1 into ethanol dispersion liquid, uniformly mixing, putting into a ball milling tank, crushing by using a ball mill at a rotation speed of 1200r/min, taking out, centrifuging, washing and drying to obtain graphene nano sheets, and using the graphene nano sheets as anode materials of lithium ion batteries and sodium ion batteries.
Example 3:
S1, respectively adding 1.2g of tin sulfate and 0.60g of potassium oxalate into two beakers filled with 20mL of ethylene glycol, performing ultrasonic dissolution to obtain a reaction solution, then dropwise adding an oxalic acid solution into an ethanol solution of tin dichloride at a rate of 0.75mL/min, and stirring a magnet at a rotating speed of 550r/min to obtain a tin oxalate micron hollow tube;
S2, adding the tin oxalate hollow micron hollow tube obtained in the step S1 into ethylene glycol dispersion liquid, uniformly mixing, putting into a ball milling tank, crushing by using a ball mill at a rotating speed of 1140r/min, taking out, centrifuging, washing and drying to obtain graphene nano sheets, and using the graphene nano sheets as anode materials of lithium ion batteries and sodium ion batteries.
The following are test results for the samples prepared in examples 1-3:
1. The SEM image and TEM image of the tin oxalate micro hollow tube prepared in example 1 are shown in fig. 1, and it can be seen from the image that the size of the tin oxalate micro hollow tube prepared in example 1 is 2-3 μm. SEM images and TEM images of tin oxalate micro hollow tubes prepared in examples 2 to 4 were very similar to those of fig. 1, and the dimensions were also 2 to 3 μm, so that they were omitted.
2. An SEM image and a TEM image of the lithium and sodium storage material of the tin oxalate nanosheets prepared in example 1 are shown in FIG. 2, and it can be seen from the images that the size of the tin oxalate nanosheets prepared in example 1 is 100-600 nm. SEM and TEM images of the lithium and sodium storage materials of tin oxalate nanosheets prepared in examples 2 to 4 are very similar to those of FIG. 2, and the dimensions are also 100 to 600nm, so that the materials are omitted.
3. The XRD pattern of the lithium and sodium oxalate material of the tin oxalate nanosheets prepared in example 1 is shown in fig. 3, and diffraction peaks of tin oxalate can be seen from the figure, and X-ray diffraction tests are also performed on the tin oxalate micro hollow tubes and tin oxalate nanosheets prepared in examples 2 to 4, and the test results are the same as those of fig. 3, so that the diffraction peaks are omitted.
4. The test results of the cycling stability of the tin oxalate hollow micrometer hollow tube and tin oxalate nanosheet lithium ion battery cathode material prepared in the embodiment 1 are shown in fig. 4,5 and 6, and as can be seen from the fig. 4, the battery capacity of the tin oxalate nanosheet lithium ion battery cathode material prepared in the embodiment 1 after 50 charge and discharge cycles is 982 mAh g -1 under the current density of 100 mA g -1, and the initial coulomb efficiency is 65.3%; as can be seen from fig. 5, the tin oxalate nanosheet lithium ion battery anode material prepared in example 1 still has a reversible capacity of 1300 mAh g -1 after 600 cycles at a current density of 1000mA g -1; as can be seen from fig. 6, the tin oxalate nanoplatelets lithium ion battery anode material prepared in example 1 has reversible capacities of 900, 750, 737, 688, 677 and mAh g -1 at 100, 200, 500, 1000, 2000mA g -1, respectively, and has a capacity retention of 64% even at a high current density of 2000mA g -1, and has a reversible capacity of 845mAh g -1 when the current returns to 1C. The negative electrode material of the tin oxalate nanosheet lithium ion battery prepared in the embodiment 1 of the invention has excellent cycle stability and rate capability, and has great practical application value.
5. The stability test result of the tin oxalate nanosheet sodium ion battery anode material prepared in example 1 is shown in fig. 7, and it can be seen from fig. 7 that, when the tin oxalate nanosheet prepared in example 1 is used as the sodium ion battery anode material, the battery capacity after 50 cycles of charge and discharge is 355mAh g -1 under the current density of 50mA g -1, and the first coulomb efficiency is 45.3%. The tin oxalate nanosheets prepared in examples 2 to 4 were also subjected to a cycle stability test as a negative electrode material for sodium ion batteries, and the test results were substantially the same as those in fig. 7, and therefore omitted.
6. The test result of the cycle stability of the tin oxalate nanosheet lithium ion battery anode material prepared in example 2 is shown in fig. 8, and it can be seen from fig. 8 that the tin oxalate nanosheet lithium ion battery anode material prepared in example 2 still has a reversible capacity of 967 mAh g -1 after 500 cycles at a current density of 1000mA g -1.
7. The test result of the cycle stability of the tin oxalate nanosheet lithium ion battery anode material prepared in example 3 is shown in fig. 9, and it can be seen from fig. 9 that the tin oxalate nanosheet lithium ion battery anode material prepared in example 3 still has a reversible capacity of 1005 mAh g -1 after 500 cycles at a current density of 1000mA g -1.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.

Claims (7)

1. The preparation method of the nano flaky tin oxalate high-performance lithium and sodium storage material is characterized by comprising the following steps of:
s1, respectively dissolving oxalic acid or oxalate and tin salt to obtain oxalic acid or oxalate solution and tin salt solution, and then dropwise adding the oxalic acid or oxalate solution into the tin salt solution under stirring at a certain rate to obtain tin oxalate micrometer hollow tubes;
s2, adding the tin oxalate micron hollow tubes obtained in the step S1 into the dispersion liquid, uniformly mixing, crushing, centrifuging, washing and drying to obtain the nano flaky tin oxalate high-performance lithium and sodium storage material;
The oxalate is sodium oxalate or potassium oxalate;
The tin oxalate micron hollow tube in the step S2 is crushed by ball milling, and the used dispersion liquid is one or more of ultrapure water, ethanol and ethylene glycol;
The tin salt is tin dichloride or stannous sulfate.
2. The nano flaky tin oxalate high-performance lithium and sodium storage material according to claim 1, which is characterized in that: the oxalic acid or the solvent in the oxalate solution and the tin salt solution is one or a mixture of more of ethanol, glycerol, ethylene glycol and dimethylformamide.
3. The nano flaky tin oxalate high-performance lithium and sodium storage material according to claim 1, which is characterized in that: in the step S1, the tin salt is tin dichloride, oxalic acid is dissolved to obtain oxalic acid solution, and the molar ratio of tin dichloride to oxalic acid is 1: 1-2.
4. The nano flaky tin oxalate high-performance lithium and sodium storage material according to claim 1, which is characterized in that: during tin oxalate ball milling, the rotating speed of the ball mill is 920-1200r/min, and the ball milling time of the ball mill is 2-6 h.
5. A battery assembled with the nano sheet-shaped tin oxalate high-performance lithium and sodium storage material according to any one of claims 1 to 4, wherein the nano sheet-shaped tin oxalate high-performance lithium and sodium storage material is used as a negative electrode material.
6. The battery according to claim 5, wherein: the battery is a lithium ion battery or a sodium ion battery.
7. The battery according to claim 6, characterized in that the preparation method thereof comprises the steps of:
(A) Weighing a nano flaky tin oxalate high-performance lithium and sodium storage material, acetylene black and sodium alginate, adding a proper amount of distilled water, uniformly mixing, grinding and stirring to form paste, and coating the paste on a copper foil;
(B) And drying, slicing, assembling and tabletting the copper foil coated with the tin oxalate negative electrode material to obtain the lithium ion battery or the sodium ion battery.
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