CN117756087A - Preparation method of negative electrode material for sodium ion battery and potassium ion battery - Google Patents

Preparation method of negative electrode material for sodium ion battery and potassium ion battery Download PDF

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Publication number
CN117756087A
CN117756087A CN202311715224.6A CN202311715224A CN117756087A CN 117756087 A CN117756087 A CN 117756087A CN 202311715224 A CN202311715224 A CN 202311715224A CN 117756087 A CN117756087 A CN 117756087A
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negative electrode
electrode material
washing
ion battery
gluconate
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CN202311715224.6A
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白宇
宋宏芳
杨浩
赵东辉
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Fujian Xfh New Energy Materials Co ltd
Sichuan Xiangfenghua New Energy Materials Co ltd
Shanghai Xiangfenghua Technology Development Co ltd
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Fujian Xfh New Energy Materials Co ltd
Sichuan Xiangfenghua New Energy Materials Co ltd
Shanghai Xiangfenghua Technology Development Co ltd
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Priority to CN202311715224.6A priority Critical patent/CN117756087A/en
Publication of CN117756087A publication Critical patent/CN117756087A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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Abstract

The invention discloses a preparation method of a negative electrode material for a sodium ion battery and a potassium ion battery, which comprises the following steps of: mixing the materials, preheating, washing and carbonizing to obtain the cathode material. The negative electrode material is prepared by taking starch and gluconate as main raw materials through simple mixing, preheating treatment, acid washing and high-temperature carbonization, has the advantages of high gram capacity, high first efficiency and high capacity retention rate, and can be applied to sodium ion or potassium ion batteries.

Description

Preparation method of negative electrode material for sodium ion battery and potassium ion battery
Technical Field
The invention relates to the technology in the field of cathodes, in particular to a preparation method of a cathode material for sodium ion batteries and potassium ion batteries.
Background
In recent years, environmental problems are increasingly raised due to carbon emissions from fossil energy consumption, and the development of renewable energy sources such as solar energy, wind energy, tidal energy and the like on a large scale has become a global important consensus for advancing energy consumption structures toward low carbonization and cleaning. Since the commercialization of SONY in the 90 th century, lithium ion batteries have been widely used in the fields of mobile electronic devices, electric vehicles, and the like. With the increasingly wide application of lithium ion batteries, lithium resources with insufficient reserves in the crust will not meet the increasing huge demand, so the development of other battery technologies capable of effectively replacing lithium ion batteries in the energy storage field is urgent. Sodium and potassium resources are very abundant and distributed uniformly, and sodium, potassium and lithium are the same main group elements and have similar chemical properties, so that the development of sodium ion and potassium ion batteries can be used for referencing the successful experience of lithium ion batteries.
The most promising materials for large scale negative electrodes for sodium and potassium ion batteries are hard carbon materials. The microstructure of the hard carbon is short-range ordered micro-regions stacked by curved graphite-like sheets, and the random stacking of each micro-region leaves more nano holes. Because it tends to have a larger interlayer spacing (typically greater than 0.37 nm), more nanopores, and more defect sites, more sodium or potassium ions can be stored, with higher specific capacity. The performance of the hard carbon material on sodium ion or potassium ion batteries is still in the development stage, and physicochemical indexes such as granularity, specific surface, ash content and interlayer spacing are also limiting the capacity and first effect of the hard carbon material. Therefore, there is a need to propose a new solution to the above-mentioned problems.
Disclosure of Invention
In view of the above, the present invention aims at overcoming the drawbacks of the prior art, and its main objective is to provide a method for preparing a negative electrode material for sodium ion battery and potassium ion battery, wherein the prepared negative electrode material has the advantages of high gram capacity, high first efficiency and high capacity retention rate.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the negative electrode material for the sodium ion battery and the potassium ion battery comprises the following steps:
(1) Mixing materials: starch and gluconate are mixed according to the mass ratio of 1: mixing the materials in the proportion of (0.5-1.5) in a stirrer to obtain mixed powder;
(2) Preheating: placing the mixed powder obtained in the step (1) into a crucible, then placing the crucible into a muffle furnace, heating to 200-400 ℃ at a heating rate of 5-10 ℃/min under the atmosphere of protective gas, and preserving heat for 2-3h to obtain a precursor;
(3) Washing: washing the precursor obtained in the step (2) for 3-8 times by using pickling solution, washing with water until the pH value is neutral, and drying to obtain a pickled precursor;
(4) Carbonizing: and (3) placing the precursor obtained in the step (3) in a crucible, heating to 1000-1300 ℃ at a heating rate of 5-15 ℃/min under the atmosphere of protective gas, preserving heat for 2-4h, cooling to room temperature, and grinding into powder to obtain the negative electrode material.
As a preferred scheme, the gluconate is one or more of magnesium gluconate, zinc gluconate and calcium gluconate.
As a preferable scheme, the shielding gas is one or more of nitrogen, argon, helium and neon.
As a preferable scheme, the pickling solution is one or a mixture of more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and in particular, the technical scheme can be as follows:
the negative electrode material is prepared by taking starch and gluconate as main raw materials through simple mixing, preheating treatment, acid washing and high-temperature carbonization, has the advantages of high gram capacity, high first efficiency and high capacity retention rate, and can be applied to sodium ion or potassium ion batteries.
In order to more clearly illustrate the structural features and efficacy of the present invention, the following detailed description of the invention is made with reference to the accompanying drawings and to the specific embodiments:
drawings
FIG. 1 is a scanning electron microscope image of the anode material prepared in example 1 of the present invention at different resolutions;
FIG. 2 is a scanning electron microscope image of the anode material prepared in example 2 of the present invention at different resolutions;
FIG. 3 is a scanning electron microscope image of the anode material prepared in example 3 of the present invention at different resolutions;
FIG. 4 is a scanning electron microscope image of the anode material prepared in example 4 of the present invention at different resolutions;
FIG. 5 is a scanning electron microscope image of the anode material prepared in example 5 of the present invention at different resolutions;
FIG. 6 is a scanning electron microscope image of the anode material prepared in example 6 of the present invention at different resolutions.
Detailed Description
The invention discloses a preparation method of a negative electrode material for a sodium ion battery and a potassium ion battery, which comprises the following steps:
(1) Mixing materials: starch and gluconate are mixed according to the mass ratio of 1: mixing (0.5-1.5) with magnesium gluconate, zinc gluconate and/or calcium gluconate to obtain mixed powder.
(2) Preheating: placing the mixed powder obtained in the step (1) into a crucible, then placing the crucible into a muffle furnace, heating to 200-400 ℃ at a heating rate of 5-10 ℃/min under the atmosphere of protective gas, and preserving heat for 2-3h to obtain a precursor; wherein the protective gas is one or more of nitrogen, argon, helium and neon.
(3) Washing: washing the precursor obtained in the step (2) for 3-8 times by using pickling solution, washing with water until the pH value is neutral, and drying to obtain a pickled precursor; the pickling solution is one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
(4) Carbonizing: placing the precursor obtained in the step (3) in a crucible, heating to 1000-1300 ℃ at a heating rate of 5-15 ℃/min under the atmosphere of protective gas, preserving heat for 2-4 hours, cooling to room temperature, and grinding into powder to obtain a negative electrode material; wherein the protective gas is one or more of nitrogen, argon, helium and neon.
The following describes in detail specific embodiments.
Example 1
(1) Mixing materials: starch and magnesium gluconate are mixed according to the mass ratio of 1:1 are put into a stirrer to be uniformly mixed, thus obtaining mixed powder.
(2) Preheating: and (3) placing the mixed powder obtained in the step (1) into a crucible, placing the crucible into a muffle furnace, heating to 400 ℃ at a heating rate of 10 ℃/min under the atmosphere of argon, and preserving heat for 2 hours to obtain the precursor.
(3) Washing: and (3) washing the precursor obtained in the step (2) for 3 times by using a mixed solution of nitric acid and sulfuric acid, washing with water until the pH value is neutral, and drying to obtain the acid-washed precursor.
(4) Carbonizing: and (3) placing the precursor obtained in the step (3) in a crucible, heating to 1000 ℃ at a heating rate of 10 ℃/min under the atmosphere of argon, preserving heat for 2 hours, cooling to room temperature, and grinding into powder to obtain the anode material.
Example 2
(1) Mixing materials: starch and zinc gluconate are mixed according to the mass ratio of 1:1.5, and mixing the materials uniformly in a stirrer to obtain mixed powder.
(2) Preheating: and (3) placing the mixed powder obtained in the step (1) into a crucible, placing the crucible into a muffle furnace, heating to 300 ℃ at a heating rate of 8 ℃/min under the atmosphere of nitrogen and argon, and preserving heat for 2 hours to obtain the precursor.
(3) Washing: and (3) washing the precursor obtained in the step (2) for 8 times by using hydrochloric acid, washing with water until the pH is neutral, and drying to obtain the acid-washed precursor.
(4) Carbonizing: and (3) placing the precursor obtained in the step (3) in a crucible, heating to 1200 ℃ at a heating rate of 10 ℃/min under the atmosphere of nitrogen and argon, preserving heat for 4 hours, cooling to room temperature, and grinding into powder to obtain the anode material.
Example 3
(1) Mixing materials: starch and calcium gluconate are mixed according to the mass ratio of 1: mixing in a mixer to obtain mixed powder at a ratio of 0.5.
(2) Preheating: and (3) placing the mixed powder obtained in the step (1) into a crucible, placing the crucible into a muffle furnace, heating to 400 ℃ at a heating rate of 5 ℃/min under the atmosphere of helium, and preserving heat for 3 hours to obtain a precursor.
(3) Washing: and (3) washing the precursor obtained in the step (2) for 5 times by using phosphoric acid, washing with water until the pH is neutral, and drying to obtain the acid-washed precursor.
(4) Carbonizing: and (3) placing the precursor obtained in the step (3) in a crucible, heating to 1300 ℃ at a heating rate of 5 ℃/min under the atmosphere of helium, preserving heat for 4 hours, cooling to room temperature, and grinding into powder to obtain the anode material.
Example 4
(1) Mixing materials: starch, zinc gluconate and calcium gluconate are mixed according to the mass ratio of 1: mixing in a mixer to obtain mixed powder at a ratio of 0.8.
(2) Preheating: and (3) placing the mixed powder obtained in the step (1) into a crucible, placing the crucible into a muffle furnace, heating to 200 ℃ at a heating rate of 6 ℃/min under the atmosphere of neon, and preserving heat for 3 hours to obtain the precursor.
(3) Washing: and (3) washing the precursor obtained in the step (2) for 6 times by using phosphoric acid, washing with water until the pH is neutral, and drying to obtain the acid-washed precursor.
(4) Carbonizing: and (3) placing the precursor obtained in the step (3) in a crucible, heating to 1300 ℃ at a heating rate of 15 ℃/min under the atmosphere of neon, preserving heat for 3.5 hours, cooling to room temperature, and grinding into powder to obtain the anode material.
Example 5
(1) Mixing materials: starch and magnesium gluconate and zinc gluconate are mixed according to the mass ratio of 1:1.2, and uniformly mixing the materials in a stirrer to obtain mixed powder.
(2) Preheating: and (3) placing the mixed powder obtained in the step (1) into a crucible, placing the crucible into a muffle furnace, heating to 350 ℃ at a heating rate of 8 ℃/min under the atmosphere of helium, and preserving heat for 3 hours to obtain a precursor.
(3) Washing: and (3) washing the precursor obtained in the step (2) for 8 times by using a mixed solution of hydrochloric acid and phosphoric acid, washing with water until the pH value is neutral, and drying to obtain the acid-washed precursor.
(4) Carbonizing: and (3) placing the precursor obtained in the step (3) into a crucible, heating to 1300 ℃ at a heating rate of 12 ℃/min under the atmosphere of neon, preserving heat for 4 hours, cooling to room temperature, and grinding into powder to obtain the anode material.
Example 6
(1) Mixing materials: the starch, magnesium gluconate, zinc gluconate and calcium gluconate are mixed according to the mass ratio of 1:1.4, and uniformly mixing the materials in a stirrer to obtain mixed powder.
(2) Preheating: and (3) placing the mixed powder obtained in the step (1) into a crucible, placing the crucible into a muffle furnace, heating to 380 ℃ at a heating rate of 6 ℃/min under the atmosphere of helium, and preserving heat for 3 hours to obtain a precursor.
(3) Washing: and (3) washing the precursor obtained in the step (2) for 8 times by using a mixed solution of hydrochloric acid and phosphoric acid, washing with water until the pH value is neutral, and drying to obtain the acid-washed precursor.
(4) Carbonizing: and (3) placing the precursor obtained in the step (3) in a crucible, heating to 1250 ℃ at a heating rate of 6 ℃/min under the atmosphere of neon, preserving heat for 3 hours, cooling to room temperature, and grinding into powder to obtain the anode material.
The negative electrode materials prepared in the above examples were subjected to performance test, and the test results are shown in table 1.
Table 1.
As can be seen from the table, the negative electrode material prepared by the preparation method provided by the invention has the advantages of high gram capacity, high first efficiency and high capacity retention rate, can be applied to sodium ion or potassium ion batteries, and has good specific volume value performance in the application of super capacitors.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical principles of the present invention are still within the scope of the technical solutions of the present invention.

Claims (4)

1. A preparation method of a negative electrode material for a sodium ion battery and a potassium ion battery is characterized by comprising the following steps: the method comprises the following steps:
(1) Mixing materials: starch and gluconate are mixed according to the mass ratio of 1: mixing the materials in the proportion of (0.5-1.5) in a stirrer to obtain mixed powder;
(2) Preheating: placing the mixed powder obtained in the step (1) into a crucible, then placing the crucible into a muffle furnace, heating to 200-400 ℃ at a heating rate of 5-10 ℃/min under the atmosphere of protective gas, and preserving heat for 2-3h to obtain a precursor;
(3) Washing: washing the precursor obtained in the step (2) for 3-8 times by using pickling solution, washing with water until the pH value is neutral, and drying to obtain a pickled precursor;
(4) Carbonizing: and (3) placing the precursor obtained in the step (3) in a crucible, heating to 1000-1300 ℃ at a heating rate of 5-15 ℃/min under the atmosphere of protective gas, preserving heat for 2-4h, cooling to room temperature, and grinding into powder to obtain the negative electrode material.
2. The method for producing a negative electrode material for sodium ion batteries and potassium ion batteries according to claim 1, characterized in that: the gluconate is one or more of magnesium gluconate, zinc gluconate and calcium gluconate.
3. The method for producing a negative electrode material for sodium ion batteries and potassium ion batteries according to claim 1, characterized in that: the protective gas is one or more of nitrogen, argon, helium and neon.
4. The method for producing a negative electrode material for sodium ion batteries and potassium ion batteries according to claim 1, characterized in that: the pickling solution is one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.
CN202311715224.6A 2023-12-13 2023-12-13 Preparation method of negative electrode material for sodium ion battery and potassium ion battery Pending CN117756087A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118099357A (en) * 2024-04-22 2024-05-28 山东方诺新材料科技有限公司 Sodium ion battery and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118099357A (en) * 2024-04-22 2024-05-28 山东方诺新材料科技有限公司 Sodium ion battery and preparation method thereof

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