CN115125069A - Acid washing detergent for positive electrode material of sodium-ion battery and application thereof - Google Patents

Acid washing detergent for positive electrode material of sodium-ion battery and application thereof Download PDF

Info

Publication number
CN115125069A
CN115125069A CN202210969270.8A CN202210969270A CN115125069A CN 115125069 A CN115125069 A CN 115125069A CN 202210969270 A CN202210969270 A CN 202210969270A CN 115125069 A CN115125069 A CN 115125069A
Authority
CN
China
Prior art keywords
acid
sodium
positive electrode
organic acid
electrode material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210969270.8A
Other languages
Chinese (zh)
Other versions
CN115125069B (en
Inventor
肖长喜
詹新举
刘应春
王媛
刘萌萌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhu Etc Battery Ltd
Original Assignee
Wuhu Etc Battery Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhu Etc Battery Ltd filed Critical Wuhu Etc Battery Ltd
Priority to CN202210969270.8A priority Critical patent/CN115125069B/en
Publication of CN115125069A publication Critical patent/CN115125069A/en
Application granted granted Critical
Publication of CN115125069B publication Critical patent/CN115125069B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/265—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 discloses an acid washing detergent for a sodium ion battery anode material and application thereof; the acid washing detergent contains water, an organic solvent and an organic acid. The pickling detergent is efficient, has no negative influence, and reduces the surface alkali content in the sodium ion positive electrode material.

Description

Acid washing detergent for positive electrode material of sodium-ion battery and application thereof
Technical Field
The invention relates to the field of sodium ion batteries, in particular to an acid washing detergent for a sodium ion battery anode material and application thereof.
Background
The lithium ion battery is an important energy storage device of the current mobile electronic equipment, new energy electric automobile and the like, and is a secondary battery which is generally accepted as the most influential at present due to the characteristics of high energy density, long cycle life and the like. The advent of the dual carbon target and the continued decline in lithium battery costs enabled the large-scale commissioning of grid-side projects, with a trillion market of stored energy emerging in 2021. Despite good cycle performance and long service life, the fact that the content of lithium ore resources is only 0.0065% worldwide is faced, and in addition, excessive exploitation in recent years causes the lithium resources to be in danger of exhaustion, so that people need to demand a new material to replace the lithium resources.
In the 1970 s and lithium ion batteries, sodium and lithium are in the same main group of the periodic table and have similar physicochemical properties, and the global sodium resource storage is more than 2.64% and 400 times of the lithium resource. Meanwhile, the sodium ion compound is easy to obtain, stable in price and low in price; sodium and aluminum do not alloy under low voltage. Therefore, sodium ion batteries have great potential for large-scale applications.
Because the performance of the lithium ion battery is too excellent, the sodium ion battery is gradually developed in the 2010 and has a hot trend, and on the basis of the lithium ion battery, the sodium ion battery only takes 10 years to develop a small scale.
The sodium ion anode material mainly comprises layered metal oxide, Prussian blue and polyanion; as sodium carbonate is mainly used as a sodium source in the production process of the sodium ion cathode material, the alkali content of the sodium ion cathode material is high. Meanwhile, the sodium ion anode material is easier to react with CO in the air 2 、H 2 The reaction of O will form NaOH and Na on the surface of the material 2 CO 3 I.e. surface residual alkali. Since the sodium ion cathode material homogenate uses polyvinylidene fluoride (PVDF) as a binder, PVDF under alkaline conditions can gel the slurry and thus cannot be coated during the homogenate and coating process.
Disclosure of Invention
The invention aims to provide an acid washing detergent for a sodium ion battery positive electrode material and application thereof.
In order to achieve the purpose, the invention provides an acid-washing detergent for a positive electrode material of a sodium-ion battery, which contains water, an organic solvent and an organic acid.
Preferably, the weight ratio of the water, the organic solvent and the organic acid is 40-80: 10-45: 1-10.
Preferably, the organic solvent is selected from at least one of C1-C4 alcohol solvents and C2-C10 carboxylic ester solvents;
preferably, the alcohol solvent is selected from at least one of methanol and ethanol;
preferably, the carboxylic ester solvent is selected from at least one of ethyl acetate, ethyl formate, hexyl propionate and propyl acetate;
more preferably, the organic solvent is ethyl acetate or ethanol.
Preferably, the organic acid is at least one selected from the group consisting of a monobasic organic acid, a dibasic organic acid, and a polybasic organic acid (which means an organic acid having three or more carboxyl groups);
preferably, the monobasic organic acid is C2-C8 organic acid, and is selected from at least one of formic acid, acetic acid and propionic acid, and is more preferably acetic acid;
preferably, the dibasic organic acid and the polybasic organic acid are C2-C8 organic acids, and are selected from at least one of citric acid, oxalic acid, tartaric acid and malic acid, and preferably citric acid.
Preferably, the organic acid contains a monobasic organic acid and a polybasic organic acid, and the weight ratio of the monobasic organic acid to the polybasic organic acid is (1-5): (1-5);
preferably, the organic acid contains (1-5) by weight: (1-5) acetic acid and citric acid.
The invention further provides an application of the acid washing detergent for the positive electrode material of the sodium-ion battery in cleaning the positive electrode material of the sodium-ion battery.
Preferably, the method for cleaning the sodium ion cathode material comprises the following steps: dispersing the sodium ion positive electrode material in the acid washing detergent according to any one of claims 1 to 5, followed by filtration and drying.
Preferably, the molar weight of the residual alkali on the surface of the sodium ion cathode material is M1, the molar weight of the acid in the acid-washing detergent is M2, and the ratio of M2 to M1 is 1: 0.8-1.0;
wherein the molar weight of the acid in the acid washing detergent is the molar weight of the total hydrogen ions after all the hydrogen ions of all the default acids can be dissociated; the molar quantity of the residual alkali on the surface of the sodium ion positive electrode material refers to the sum of the molar quantities of sodium ions contained in sodium carbonate, sodium bicarbonate and sodium hydroxide in the sodium ion positive electrode material.
Preferably, the dispersing further comprises a stirring process, the stirring process satisfying at least the following conditions: the rotating speed is 500-880r/min, and the time is 10-60 min.
Preferably, the drying is vacuum drying, and at least the following conditions are met: the temperature is 60-130 ℃, and the time is 180-480 min.
In the technical scheme, the surface alkali content in the sodium ion anode material is reduced through experimental exploration, and the phenomenon of gel in the homogenization process of the sodium ion anode material is weakened or avoided. The technical scheme recorded in the invention is obtained through continuous tests.
Firstly, the species of residual alkali in the sodium ion positive electrode material is analyzed, and the species is mainly Na 2 CO 3 、NaHCO 3 NaOH is also the main reason for generating gel in the process of homogenizing the sodium ion anode material, and the method can effectively reduce the content of residual alkali in the sodium ion anode material and avoid the gel phenomenon in the process of homogenizing the sodium ion anode material.
Wherein, in the acid-washing detergent, water is used as a carrier for the dissociation of the organic solvent and the organic acid, so that the organic acid and the water have acidic reaction; the organic solvent is used as a solubilizer, can be mutually soluble with water in any proportion, has an excellent infiltration effect, increases the solubility of organic acid in water, and is low in boiling point and easy to remove at the later stage; in addition, the addition of the organic solvent and the organic acid can effectively inhibit the precipitation of sodium ions in the material and the generation of Na2CO3 on the surface of the material.
In conclusion, the invention has the following advantages:
1. the invention can effectively reduce the alkalinity of the sodium ion anode material, so that the prepared anode material has extremely low residual sodium content;
2. the acid washing detergent is a formula obtained through continuous experimental optimization, is weak in acidity, cannot influence the characteristics of a sodium ion material, and has no negative influence on a product;
3. the components of the pickling detergent disclosed by the invention are common substances in a laboratory, and the pickling detergent is safe, non-toxic, low in price, easy to obtain and convenient to use.
4. The acid washing detergent can effectively improve the processability of the sodium ion anode material, and is suitable for industrial production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
fig. 1 is a comparative graph of specific capacity-voltage curves of button cells assembled before and after washing of sodium ion positive electrode materials (using the detergent of example 1);
FIG. 2 is a photograph of a shot of the powder before washing the sodium ion positive electrode material (using the detergent of example 1);
FIG. 3 is a photograph of a shot of the powder after washing the sodium ion positive electrode material (using the detergent of example 1).
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides an acid washing detergent for a positive electrode material of a sodium-ion battery, which contains water, an organic solvent and organic acid.
In addition, in the invention, the preparation method of the acid washing detergent only needs to mix the components.
In the present invention, the amount of each material may be selected within a wide range, but in order to further enhance the pickling effect of the detergent, it is preferable that the weight ratio of the water, the organic solvent and the organic acid is 40 to 80: 10-45: 1-10; more preferably, the weight ratio of water, organic solvent and organic acid is 40-80: 10-45: 5-10.
In the present invention, the kind of the organic solvent may be selected from a wide range, but in order to further improve the acid washing effect of the detergent, it is preferable that the organic solvent is selected from at least one of alcohol solvents of C1 to C4, carboxylic ester solvents of C2 to C10.
In addition to the above embodiments, the kind of the alcohol solvent may be selected from a wide range, but in order to further improve the acid washing effect of the detergent, it is preferable that the alcohol solvent is selected from at least one of methanol and ethanol.
On the basis of the above embodiment, the kind of the carboxylic ester solvent may be selected from a wide range, but in order to further improve the pickling effect of the detergent, it is preferable that the carboxylic ester solvent is selected from at least one of ethyl acetate, ethyl formate, hexyl propionate, and propyl acetate.
In addition to the above embodiments, it is more preferable that the organic solvent is ethyl acetate or ethanol. The ethyl acetate is used as a solubilizer, can be mutually soluble with most organic solvents in any proportion, has an excellent infiltration effect, increases the solubility of acetic acid and citric acid in water, and is low in boiling point and easy to remove in the later period.
In the present invention, the kind of the organic acid may be selected from a wide range, but in order to further improve the pickling effect of the detergent, it is preferable that the organic acid is at least one selected from the group consisting of a mono-organic acid, a di-organic acid, and a poly-organic acid (which means an organic acid containing three or more carboxyl groups).
In addition to the above embodiments, the kind of the monobasic organic acid may be selected from a wide range, but in order to further improve the acid washing effect of the detergent, the monobasic organic acid is preferably an organic acid of C2 to C8, and is selected from at least one of formic acid, acetic acid, and propionic acid, and more preferably acetic acid; compared with general inorganic acid, acetic acid is a unitary organic weak acid, and the acid corrosivity is milder than that of the inorganic acid, so that the influence of acid washing on the structure of the sodium ion positive electrode material can be reduced, and the removal degree of alkalinity in the sodium ion positive electrode material can be well controlled.
In addition to the above embodiments, the kinds of the dibasic organic acid and the polybasic organic acid may be selected from a wide range, but in order to further improve the pickling effect of the detergent, the dibasic organic acid and the polybasic organic acid are preferably C2 to C8 organic acids, and are selected from at least one of citric acid, oxalic acid, tartaric acid, and malic acid, and are preferably citric acid. Citric acid is a strong ternary organic acid, but has extremely slow and small corrosion to metals, is often used as an acidity regulator due to different degrees of tertiary hydrolysis, and is a safe washing additive.
In addition to the above embodiments, in order to further improve the pickling effect of the detergent, it is preferable that the organic acid contains a monovalent organic acid and a polyvalent organic acid in a weight ratio of (1 to 5): (1-5); more preferably, the organic acid contains (1-5) by weight: (1-5) acetic acid and citric acid.
The invention further provides application of the acid washing detergent for the sodium ion battery positive electrode material in cleaning of the sodium ion positive electrode material.
In the above application, the method for cleaning the sodium ion positive electrode material may be selected from a wide range, but in order to improve the pickling effect, preferably, the method for cleaning the sodium ion positive electrode material includes: dispersing the sodium ion positive electrode material in the acid washing detergent according to any one of claims 1 to 5, followed by filtration and drying.
In the above embodiment, the amount of the acid washing detergent may be selected from a wide range, but in order to further improve the acid washing effect, it is preferable that the molar amount of the surface residual alkali of the sodium ion positive electrode material is M1, the molar amount of the acid in the acid washing detergent is M2, and the ratio of M2 to M1 is 1: 0.8-1.0; wherein the molar weight of the acid in the acid washing detergent is the molar weight of the total hydrogen ions after all the hydrogen ions of all the default acids can be dissociated; the molar quantity of the residual alkali on the surface of the sodium ion cathode material refers to the sum of the molar quantities of sodium ions contained in sodium carbonate, sodium bicarbonate and sodium hydroxide in the sodium ion cathode material.
In the above embodiment, in order to further improve the pickling effect, it is preferable that the dispersing further includes a stirring step that satisfies at least the following conditions: the rotating speed is 500-880r/min, and the time is 10-60 min.
In the above embodiment, the conditions for the drying may be selected within a wide range, but in order to further improve the pickling effect, it is preferable that the drying is vacuum drying, and at least the following conditions are satisfied: the temperature is 60-130 ℃, and the time is 180-480 min.
The present invention will be described in detail below by way of examples.
Example 1
A detergent containing 55% of water, 40% of ethyl acetate, 3% of acetic acid and 2% of citric acid is prepared by weighing and uniformly mixing all the components, wherein the percentage of all the components refers to the weight percentage.
Example 2
The detergent containing 55% of water, 40% of ethanol, 3% of acetic acid and 2% of citric acid is prepared by weighing the components and then uniformly mixing, wherein the percentage of each component refers to the weight percentage.
Example 3
A detergent containing 55% of water, 40% of ethyl acetate, 2% of acetic acid and 3% of citric acid is prepared by weighing and uniformly mixing all the components, wherein the percentage of all the components refers to the weight percentage.
Example 4
The detergent containing 55% of water, 40% of ethanol, 3% of acetic acid and 2% of oxalic acid is prepared by weighing the components and then uniformly mixing, wherein the percentage of each component refers to the weight percentage.
Example 5
The detergent containing 55% of pure water, 40% of ethyl acetate and 5% of acetic acid is prepared by weighing the components and then uniformly mixing, wherein the percentage of each component refers to the weight percentage.
Example 6
The detergent containing 55% of pure water, 40% of ethyl acetate and 5% of citric acid is prepared by weighing the components and uniformly mixing, wherein the percentage of the components refers to the weight percentage.
Example 7
The detergent containing 45% of water, 45% of ethyl acetate, 5% of acetic acid and 5% of citric acid is prepared by weighing the components and then uniformly mixing, wherein the percentage of each component refers to the weight percentage.
Example 8
A detergent containing 80% of water, 10% of ethyl acetate, 5% of acetic acid and 5% of citric acid is prepared by weighing and uniformly mixing all the components, wherein the percentage of all the components refers to the weight percentage.
Comparative example 1
The detergent containing 60% of pure water and 40% of ethyl acetate is prepared by weighing the components and then uniformly mixing, wherein the percentage of each component refers to the weight percentage.
Comparative example 2
The detergent containing 60% of pure water, 35% of ethyl acetate and 5% of hydrochloric acid is prepared by weighing and uniformly mixing the components, wherein the percentage of each component refers to the weight percentage.
Comparative example 3
The detergent containing 90% of water, 5% of acetic acid and 5% of citric acid is prepared by weighing the components and uniformly mixing, wherein the percentage of each component refers to the weight percentage.
Application example 1
1) Taking 100g of sodium ion positive electrode material, and mixing the following raw materials in terms of residual alkali in the sodium ion positive electrode material: the molar ratio of the acids in the detergent was 0.8: 1.0, dispersing in different detergents, stirring for 30min at 660r/min, filtering, and drying for 300min at 110 ℃ in vacuum to obtain the material after acid washing.
2) The acid-washed sodium ion cathode material (5g) and ultrapure water are put into a clean and dry beaker according to the mass ratio of 1:10, are stirred magnetically at 660r/min for 3min and then are kept stand for 5min, and the pH value is measured by a calibrated or checked pH meter, and the results are shown in Table 1.
3) 5g of the sodium ion positive electrode material after acid washing was dissolved in 100mL of ultrapure water, and after suction filtration (washing with 100mL of ultrapure water) for 30min at 880r/min, the content of the residual alkali was calculated by titration with a potentiometric titrator, and the results are shown in Table 1.
4) Mixing the sodium ion positive electrode material, polyvinylidene fluoride and conductive carbon black which are subjected to acid washing according to the mass ratio of 90:5:5, using N-methyl pyrrolidone as a solvent, dispersing for 3min by using a rotation and revolution dispersion machine to obtain a flowable slurry, coating the flowable slurry on an aluminum foil with the thickness of 14 mu m by using a scraper with the thickness of 400 mu m, taking out the slurry after vacuum drying for 180min at the temperature of 110 ℃, punching a pole piece with the thickness of 14mm by using a punching machine, weighing and drying for 300min at the temperature of 110 ℃ in vacuum. The metal sodium sheet was used as a negative electrode, assembled into a CR2032 button cell in a vacuum glove box, and charged and discharged at a current of 0.1C, and the results are shown in table 1.
TABLE 1
Figure BDA0003795931080000101
In the above table, detergent-free refers to the sodium ion positive electrode material without any washing treatment.
Analysis of the above comparative examples and their test results leads to the following conclusions:
the material is only washed by pure water, although part of residual alkali on the surface can be washed away, the material is damaged to a certain extent, the specific capacity and the efficiency of the first discharge of the material are greatly reduced, and the viscosity of the slurry is too high during the subsequent pulping, so that the material is not beneficial to dispersion and coating.
The organic solvent is relatively mild and is beneficial to the dispersion of the material, and the comparative example 1 shows that the damage of water washing to the material structure can be reduced and the dispersion of the sodium ion cathode material after water washing in the pulping process can be improved by adding a certain amount of organic solvent ethyl acetate into pure water, but the content of residual alkali after water washing is still high due to the protection of the organic solvent.
The detergent in the comparative example 2 has a good acid-base neutralization effect, and greatly reduces the content of residual alkali in the sodium ion positive electrode material, but most of inorganic acid (hydrochloric acid) is too corrosive and acidic, so that the structure of the material is seriously damaged, and the capacity and the first effect of the material are greatly reduced.
Although the proportion of the organic acid was greatly increased in the detergent of comparative example 3, the detergent lacked an organic solvent to increase the mutual solubility of the organic acid and water, resulting in delamination and unfavorable dissociation of hydrogen ions in the acid, and thus the effect was not very good.
The organic acid can perform an acid reaction with water, can also neutralize alkaline substances, is weaker in corrosivity and acidity, is milder, and is relatively safe to people and equipment, and in example 5, the content of residual alkali on the surface of the sodium ion cathode material after acid washing is better than that of the sodium ion cathode material after being washed by water, but the specific discharge capacity and the discharge efficiency are reduced to some extent compared with those of the material without treatment, which indicates that the material is damaged to a certain extent.
The detergent in example 6 has limited ability to neutralize surface alkalis in the sodium ion positive electrode material because only the tribasic acid is added, and the dissociated hydrogen ions are limited.
In example 5, example 1 and example 3, we can see that the acidity of the monobasic organic acid is too strong, but the proportion of the dibasic or polybasic organic acid cannot be too high, otherwise the removal of the surface residual alkali is affected, and in example 2 and example 4, the organic solvent or the organic acid is replaced by different organic solvents, and the effect of reducing the surface residual alkali of the sodium ion cathode material can also be achieved, so that the formula (water + organic solvent + organic acid) of the detergent is feasible and effective.
In the case of the detergent in example 7, although the proportion of water is reduced, the amount of the detergent used can be reduced, the amount of the added detergent is also difficult to control, and the purpose can be achieved, but the proportion is poorer than the optimal proportion.
In the example 8, the proportion of water is increased, so that although the amount of the added washing liquid can be controlled more simply, the waste of water resources is caused, the purpose can be achieved, and the optimal proportion is poorer.
In summary, the above description and all the test results show that the most preferable scheme is the formula in example 1, the organic solvent ethyl acetate can be mutually dissolved with most of organic reagents in any proportion, the corrosivity of acetic acid and citric acid is extremely low, the safety is high, the material, human body and equipment cannot be damaged, and the effect of reducing residual alkali on the surface of the sodium ion anode material can be achieved through the specific proportion, so that the performance of the material is improved, and the method is suitable for industrial production.
In addition, fig. 1 is a comparison graph of specific capacity-voltage curves (using the detergent of example 1) of a button cell assembled before and after washing of the sodium ion positive electrode material, fig. 2 is a solid-state image of powder before washing of the sodium ion positive electrode material (using the detergent of example 1), and fig. 3 is a solid-state image of powder after washing of the sodium ion positive electrode material (using the detergent of example 1). The comparison of fig. 1 shows that the sodium ion anode material has certain improvement in electrical properties such as first discharge specific capacity and first charge-discharge efficiency after being washed with the detergent of the present invention, and the comparison of fig. 2 and fig. 3 shows that the appearance and the powder particles before and after the powder is washed are not significantly changed.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.

Claims (10)

1. The acid washing detergent for the positive electrode material of the sodium-ion battery is characterized by comprising water, an organic solvent and an organic acid.
2. The acid wash detergent according to claim 1, wherein the weight ratio of water, organic solvent and organic acid is 40-80: 10-45: 1-10.
3. The acid washing detergent as claimed in claim 1, wherein the organic solvent is at least one selected from the group consisting of C1-C4 alcohol solvents, C2-C10 carboxylic ester solvents;
preferably, the alcohol solvent is selected from at least one of methanol and ethanol;
preferably, the carboxylic ester solvent is at least one selected from ethyl acetate, ethyl formate, hexyl propionate and propyl acetate;
more preferably, the organic solvent is ethyl acetate or ethanol.
4. The acid washing detergent according to claim 1, wherein said organic acid is at least one selected from the group consisting of a monobasic organic acid, a dibasic organic acid, and a polybasic organic acid;
preferably, the monobasic organic acid is C2-C8 organic acid, and is selected from at least one of acetic acid, propionic acid and formic acid, and is more preferably acetic acid;
preferably, the dibasic organic acid and the polybasic organic acid are C2-C8 organic acids, and are selected from at least one of citric acid, oxalic acid, tartaric acid and malic acid, and preferably citric acid.
5. The acid washing detergent as claimed in claim 4, wherein said organic acid comprises a monobasic organic acid and a polybasic organic acid, and a weight ratio of said monobasic organic acid to said polybasic organic acid is (1-5): (1-5);
preferably, the organic acid contains (1-5) by weight: (1-5) acetic acid and citric acid.
6. Use of an acid washing detergent for a positive electrode material for a sodium-ion battery according to any one of claims 1 to 5 for cleaning a sodium-ion positive electrode material.
7. The use according to claim 6, wherein the method for cleaning the sodium ion positive electrode material comprises: dispersing the sodium ion positive electrode material in the acid washing detergent according to any one of claims 1 to 5, followed by filtration and drying.
8. The use of claim 7, wherein the molar amount of residual alkali on the surface of the sodium ion positive electrode material is M1, the molar amount of acid in the acid washing detergent is M2, and the ratio of M2 to M1 is 1: 0.8-1.0;
wherein the molar amount of the acid in the acid washing detergent is the molar amount of total hydrogen ions after all hydrogen ions of all the acids can be dissociated; the molar quantity of the residual alkali on the surface of the sodium ion positive electrode material refers to the sum of the molar quantities of sodium ions contained in sodium carbonate, sodium bicarbonate and sodium hydroxide in the sodium ion positive electrode material.
9. Use according to claim 7, wherein the dispersion further comprises a stirring step, the stirring step satisfying at least the following conditions: the rotating speed is 500-880r/min, and the time is 10-60 min.
10. Use according to claim 7, wherein the drying is vacuum drying, at least the following conditions being satisfied: the temperature is 60-130 ℃, and the time is 180-480 min.
CN202210969270.8A 2022-08-12 2022-08-12 Acid washing detergent for positive electrode material of sodium ion battery and application thereof Active CN115125069B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210969270.8A CN115125069B (en) 2022-08-12 2022-08-12 Acid washing detergent for positive electrode material of sodium ion battery and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210969270.8A CN115125069B (en) 2022-08-12 2022-08-12 Acid washing detergent for positive electrode material of sodium ion battery and application thereof

Publications (2)

Publication Number Publication Date
CN115125069A true CN115125069A (en) 2022-09-30
CN115125069B CN115125069B (en) 2023-11-14

Family

ID=83385051

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210969270.8A Active CN115125069B (en) 2022-08-12 2022-08-12 Acid washing detergent for positive electrode material of sodium ion battery and application thereof

Country Status (1)

Country Link
CN (1) CN115125069B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116598462A (en) * 2023-06-09 2023-08-15 巴斯夫杉杉电池材料有限公司 Layered positive electrode material of sodium ion battery and preparation method thereof

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103904317A (en) * 2012-12-25 2014-07-02 北京汉能创昱科技有限公司 Preparing method of sodium-ion battery cathode material
CN105591106A (en) * 2016-03-18 2016-05-18 宁波职业技术学院 Sodium-ion battery positive pole material and preparation method thereof
CN105938904A (en) * 2016-05-31 2016-09-14 中南大学 Composite positive electrode material for sodium-ion battery and preparation method of composite positive electrode material
WO2017000742A1 (en) * 2015-06-29 2017-01-05 山东玉皇新能源科技有限公司 Simple method for reducing ph value of lithium-ion battery ternary anode material
WO2017190365A1 (en) * 2016-05-06 2017-11-09 深圳先进技术研究院 Sodium ion battery and preparation method therefor
CN111211362A (en) * 2020-01-13 2020-05-29 北京当升材料科技股份有限公司 Lithium-supplementing washing liquid and application thereof, high-nickel multi-element positive electrode material and preparation method thereof
CN111403729A (en) * 2019-12-30 2020-07-10 上海紫剑化工科技有限公司 Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
CN111547742A (en) * 2020-04-14 2020-08-18 浙江钠创新能源有限公司 Sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery
CN112635709A (en) * 2020-12-15 2021-04-09 合肥工业大学 SEI film forming agent for negative electrode of sodium-ion battery, pre-sodium treatment method and sodium-ion battery
CN112919442A (en) * 2021-01-25 2021-06-08 中南大学 Preparation method of sodium ion battery positive electrode material sodium vanadium fluorophosphate
CN113690411A (en) * 2020-05-19 2021-11-23 溧阳中科海钠科技有限责任公司 Method for reducing pH value of positive electrode material of sodium-ion battery and application
CN114373905A (en) * 2021-12-17 2022-04-19 合肥国轩高科动力能源有限公司 Sodium ion positive electrode material and preparation method and application thereof
CN114784241A (en) * 2022-04-13 2022-07-22 河北光兴半导体技术有限公司 Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103904317A (en) * 2012-12-25 2014-07-02 北京汉能创昱科技有限公司 Preparing method of sodium-ion battery cathode material
WO2017000742A1 (en) * 2015-06-29 2017-01-05 山东玉皇新能源科技有限公司 Simple method for reducing ph value of lithium-ion battery ternary anode material
CN105591106A (en) * 2016-03-18 2016-05-18 宁波职业技术学院 Sodium-ion battery positive pole material and preparation method thereof
WO2017190365A1 (en) * 2016-05-06 2017-11-09 深圳先进技术研究院 Sodium ion battery and preparation method therefor
CN105938904A (en) * 2016-05-31 2016-09-14 中南大学 Composite positive electrode material for sodium-ion battery and preparation method of composite positive electrode material
CN111403729A (en) * 2019-12-30 2020-07-10 上海紫剑化工科技有限公司 Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery
CN111211362A (en) * 2020-01-13 2020-05-29 北京当升材料科技股份有限公司 Lithium-supplementing washing liquid and application thereof, high-nickel multi-element positive electrode material and preparation method thereof
CN111547742A (en) * 2020-04-14 2020-08-18 浙江钠创新能源有限公司 Sodium-ion battery positive electrode material, preparation method thereof and sodium-ion battery
CN113690411A (en) * 2020-05-19 2021-11-23 溧阳中科海钠科技有限责任公司 Method for reducing pH value of positive electrode material of sodium-ion battery and application
CN112635709A (en) * 2020-12-15 2021-04-09 合肥工业大学 SEI film forming agent for negative electrode of sodium-ion battery, pre-sodium treatment method and sodium-ion battery
CN112919442A (en) * 2021-01-25 2021-06-08 中南大学 Preparation method of sodium ion battery positive electrode material sodium vanadium fluorophosphate
CN114373905A (en) * 2021-12-17 2022-04-19 合肥国轩高科动力能源有限公司 Sodium ion positive electrode material and preparation method and application thereof
CN114784241A (en) * 2022-04-13 2022-07-22 河北光兴半导体技术有限公司 Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116598462A (en) * 2023-06-09 2023-08-15 巴斯夫杉杉电池材料有限公司 Layered positive electrode material of sodium ion battery and preparation method thereof

Also Published As

Publication number Publication date
CN115125069B (en) 2023-11-14

Similar Documents

Publication Publication Date Title
JP5992016B2 (en) Method for modifying lithium ion battery cathode material
CN108075111A (en) Lithium ion battery and positive electrode material thereof
CN110112388B (en) Porous tungsten trioxide coated modified positive electrode material and preparation method thereof
CN105190963A (en) Treatment process for a positive electrode active material for lithium-ion secondary battery
KR102477796B1 (en) Nonaqueous Electrolyte Secondary Battery Negative Electrode and Nonaqueous Electrolyte Secondary Battery
CN110335764B (en) Pre-sodium treatment method for efficiently constructing sodium ion capacitor
CN107785549A (en) The preparation method and carbon compound cathode materials of a kind of carbon compound cathode materials
JP2023507209A (en) Method for preparing high-density aluminum-doped cobalt oxide
CN105375023A (en) Method for removing copper and aluminum from an electrode material, and process for recycling electrode material from waste lithium-ion batteries
CN114725357B (en) Method for reducing residual sodium content of sodium ion positive electrode material
CN115763717A (en) Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery
CN113270587A (en) Preparation method and application of high-stability silicon-based composite material constructed by in-situ fluorination
CN115125069A (en) Acid washing detergent for positive electrode material of sodium-ion battery and application thereof
CN110350166A (en) A method of improving tertiary cathode material stability and processability
CN104767003B (en) Accumulator plate smear operation lead mud deepens treatment for reuse method
CN106207128A (en) A kind of Zr (OH)4the preparation method of cladding nickel cobalt aluminum tertiary cathode material
CN102583297A (en) Method for recycling lithium ion battery cathode material lithium iron phosphate
CN115939344A (en) Silane coupling agent coated modified sodium-electricity positive electrode material, preparation method and application
CN111916701A (en) Coated positive electrode material and preparation method and application thereof
CN116190634A (en) Sodium ion positive electrode material, modification method thereof, positive electrode plate and sodium ion battery
US20170256795A1 (en) Cathode material preparation method, cathode material and lithium-ion battery
CN109256556A (en) A kind of starlike Cu/Cu of the cross of core-shell structure2O/CuO@Ppy composite material and preparation method and application
CN109119257A (en) The preparation method of self-supporting nano-sheet iron cobalt boron electrode material for super capacitor
CN111477977A (en) Water-ether mixed electrolyte for lithium ion battery and preparation method thereof
CN113937249A (en) High-nickel ternary positive electrode slurry and preparation method thereof, positive electrode plate and lithium ion battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant