CN116207336A - Prussian blue sodium ion battery and preparation method thereof - Google Patents

Prussian blue sodium ion battery and preparation method thereof Download PDF

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Publication number
CN116207336A
CN116207336A CN202111454070.0A CN202111454070A CN116207336A CN 116207336 A CN116207336 A CN 116207336A CN 202111454070 A CN202111454070 A CN 202111454070A CN 116207336 A CN116207336 A CN 116207336A
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prussian blue
positive
sodium ion
active material
ion battery
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周标
高云智
石坚
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Shanghai Hanxing Technology Co ltd
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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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
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Abstract

A Prussian blue sodium ion battery and a preparation method thereof belong to the technical field of sodium ion batteries, and the specific scheme is as follows: the Prussian blue sodium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive active material layer which is arranged on the surface of the positive current collector and contains a positive active material, the water content of the positive active material layer is 0-90 mug/g, and the positive active material only plays a part in a part of a voltage platform in the charging and discharging process of the battery. The Prussian blue sodium ion battery of the invention fundamentally solves the problems of battery flatulence and electric property deterioration caused by water in the positive electrode active material. In addition, the damage to the structure of the Prussian blue positive electrode material caused by deep deintercalation of sodium ions in the charging and discharging process of the battery is weakened by controlling the deintercalation depth of the sodium ions in the Prussian blue positive electrode material, so that the long cycle performance of the sodium ion battery is realized under the condition that the Prussian blue positive electrode material is kept to have higher gram capacity.

Description

Prussian blue sodium ion battery and preparation method thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a Prussian blue sodium ion battery and a preparation method thereof.
Background
In electrochemical energy storage, lithium ion batteries have limited development in the energy storage market due to resource bottlenecks. Because electrochemical energy storage technology does not require a battery with an extremely high energy density, but rather focuses on the high safety and long life of batteries, sodium ion batteries with somewhat lower energy densities but rich resources are again of interest to researchers. Sodium ion batteries have the advantages of high safety, good rate performance, excellent low-temperature performance and the like, and are currently considered as the most potential electrochemical energy storage form. Among them, prussian blue type materials are one of the important directions of the development of the positive electrode materials of sodium ion batteries.
At present, the main stream preparation method of the sodium Prussian blue material serving as the positive electrode material of the sodium ion battery is still a chemical coprecipitation method, and the method has the advantages of low cost, simple process and the like. However, sodium Prussian blue-based materials prepared by chemical coprecipitation generally contain a large amount (about 10%) of crystal water (including coordination water and interstitial water). On one hand, the existence of the crystal water can reduce the electrochemical activity of the positive electrode material, thereby influencing the specific capacity of the positive electrode material; on the other hand, in the electrochemical reaction process of the battery, the crystal water is electrolyzed, and the secondary reaction between the crystal water and the electrolyte is easy to occur when the crystal water is added, so that the expansion and the cycle performance of the battery are reduced.
In addition, after the sodium Prussian blue material is baked to remove crystal water, the specific capacity of the sodium Prussian blue material is obviously improved, but the stability of the sodium Prussian blue material is sharply reduced, and the cycle performance of the sodium Prussian blue material is poor. The reason is that the coordination water contained in the Prussian blue material plays an important role in supporting the crystal structure of the Prussian blue material, once the coordination water in the crystal structure of the Prussian blue material is released, the crystal structure of the Prussian blue material may collapse in the sodium ion release process, so that active sites for sodium ion insertion and release are reduced, and the capacity and the cycle performance of the sodium ion battery are affected.
The positive plate disclosed in the Chinese patent No. CN 109728252A, the preparation method thereof and the sodium ion battery can reduce the probability of side reaction between coordinated water and electrolyte by controlling the water content of Prussian blue material to be 100-5000 mug/g, so that the sodium ion battery does not generate serious flatulence in the charging and discharging processes, and can be charged and discharged normally. However, the method can not fundamentally prevent the electrolysis of the crystal water and the side reaction of the crystal water and the electrolyte, thereby causing the expansion and the electric property deterioration of the battery; it is also difficult to ensure that coordinated water is not removed in the process of removing water, so that the crystal structure of the Prussian blue material is partially collapsed in the circulating process, and the circulating performance of the sodium ion battery is reduced; meanwhile, the control material keeps moderate water content, and the process control difficulty is increased to a certain extent.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a Prussian blue type sodium ion battery.
The second object of the invention is to provide a preparation method of Prussian blue sodium ion battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the Prussian blue sodium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive active material layer which is arranged on the surface of the positive current collector and contains a positive active material, the water content of the positive active material layer is 0-90 mug/g, and the positive active material only plays a part in a part of voltage platform in the charging and discharging process of the battery.
Further, by performing capacity matching on the positive electrode sheet and the negative electrode sheet and controlling the upper limit voltage and the lower limit voltage of the battery in the charging and discharging process, the positive electrode active material only plays a part of a voltage platform in the charging and discharging process of the battery.
Further, the formula for capacity matching of the positive electrode plate and the negative electrode plate is as follows: capacity per unit area of negative electrode sheet=capacity per unit area of positive electrode sheet (50% -95%) (1.0-1.5).
Further, the partial voltage platform function means that 25% -95% of the capacity of the whole voltage platform function.
Further, the positive electrode active material is Prussian blue material, and the molecular formula of the Prussian blue material is Na x M a [M b (CN) 6 ]Wherein M is a Is a transition metal, M b Is a transition metal, 0<x≤2，M a Selected from one of Fe, co, mn, cu, zn, cr, V, M b One selected from Fe, co, mn, cu, zn, cr, V.
Further, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer which is present on a surface of the negative electrode current collector and contains a negative electrode active material, and the water content of the negative electrode active material layer is 0 μg/g to 200 μg/g.
Further, the Prussian blue sodium ion battery also comprises a diaphragm, wherein the diaphragm is positioned between the positive plate and the negative plate, and the water content of the diaphragm is 0-200 mug/g.
The preparation method of the Prussian blue sodium ion battery comprises the following steps:
firstly, manufacturing a positive plate and a negative plate, and then carrying out vacuum drying treatment on the positive plate and the negative plate to control the water content of a positive electrode active material layer in the positive plate to be 0-90 mug/g;
and step two, completing lamination or winding process, assembly process, liquid injection process and packaging process of the battery in the environment with the dew point less than-45 ℃.
Further, when the battery is formed and used, the upper limit voltage and the lower limit voltage of the battery are determined according to the capacity of the unit area of the negative electrode plate of the battery, the capacity exerted by the unit area of the positive electrode plate of the battery and the area acted by the positive electrode active material voltage platform.
Compared with the prior art, the invention has the beneficial effects that:
according to the Prussian blue sodium ion battery, the positive electrode active material is Prussian blue material, and the water content of the positive electrode active material layer is 0-90 mug/g, so that the water in the positive electrode active material is prevented from being electrolyzed in the charge-discharge process, and the side reaction between the water in the positive electrode active material and electrolyte is prevented, and the problems of battery gassing and electrical property deterioration caused by the water in the positive electrode active material are fundamentally solved. In addition, the damage to the structure of the Prussian blue positive electrode material caused by deep deintercalation of sodium ions in the charging and discharging process of the battery is weakened by controlling the deintercalation depth of the sodium ions in the Prussian blue positive electrode material, so that the long cycle performance of the sodium ion battery is realized under the condition that the Prussian blue positive electrode material is kept to have higher gram capacity.
The Prussian blue sodium ion battery provided by the invention has the advantages of simple manufacturing process, easiness in controlling key factors and convenience in large-scale industrial production.
Drawings
Fig. 1 is a graph of charge-discharge voltage versus specific capacity for circle 1 of the battery prepared in example 1;
fig. 2 is a graph of charge-discharge voltage versus specific capacity for the battery prepared in example 1 at cycle 2;
fig. 3 is a graph showing comparison of the capacity retention curves of the batteries prepared in example 1 and comparative example 1;
fig. 4 is a graph showing the charge-discharge voltage vs. specific capacity at 1 st turn of the battery prepared in comparative example 1;
fig. 5 is a graph showing the charge-discharge voltage vs. specific capacity at cycle 1 of the battery prepared in example 3;
fig. 6 is a graph showing comparison of the capacity retention curves of the batteries prepared in example 3 and comparative example 3;
fig. 7 is a graph showing the charge-discharge voltage vs. specific capacity at cycle 1 of the battery prepared in comparative example 3;
Detailed Description
The invention will now be described in detail with reference to figures 1-7 and the accompanying examples.
Detailed description of the preferred embodiments
The Prussian blue sodium ion battery comprises a positive plate, a negative plate, electrolyte, a diaphragm and a packaging shell, wherein the positive plate comprises a positive current collector and a positive active material layer which is arranged on the surface of the positive current collector and contains positive active materials, the water content of the positive active material layer is 0-90 mug/g, capacity matching is carried out on the positive plate and the negative plate, and the upper limit voltage and the lower limit voltage of the battery in the charging and discharging process are controlled, so that the positive active materials only act on part of a voltage platform in the charging and discharging process of the battery.
Further, the formula for capacity matching of the positive electrode plate and the negative electrode plate is as follows: capacity per unit area of negative electrode sheet=capacity per unit area of positive electrode sheet (50% -95%) (1.0-1.5).
Further, the partial voltage plateau may be at least 25% of the entire voltage plateau capacity, and at most 95% of the entire voltage plateau capacity.
Further, the positive electrode active material is Prussian blue material, and the molecular formula of the Prussian blue material is Na x M a [M b (CN) 6 ]Wherein M is a Is a transition metal, M b Is a transition metal, 0<x≤2，M a Selected from one of Fe, co, mn, cu, zn, cr, V, M b One selected from Fe, co, mn, cu, zn, cr, V.
Further, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer which is present on a surface of the negative electrode current collector and contains a negative electrode active material, and the water content of the negative electrode active material layer is 0 to 200 μg/g, preferably 0 to 100 μg/g.
Further, the negative electrode active material is a negative electrode active material used in a conventional sodium ion battery, and refers to a material having a sodium storage function and a standard electrode potential lower than that of a Prussian blue material, and the negative electrode active material includes, but is not limited to, at least one of a metal sodium simple substance, a sodium alloy and a carbon-based material. Preferably, the anode active material is sodium simple substance, snSb/C, na 2 Ti 3 O 7 Hard carbon or soft carbon.
Furthermore, the electrolyte comprises an organic solvent, sodium salt dissolved in the organic solvent, additives and the like, and the specific components and the proportion are the same as those of a conventional sodium ion battery, so that no special requirements are required; the sodium salt comprises sodium perchlorate or sodium hexafluorophosphate.
Further, the Prussian blue sodium ion battery also comprises a diaphragm, wherein the diaphragm is positioned between the positive electrode plate and the negative electrode plate, and the water content of the diaphragm is 0-200 mug/g, preferably 0-100 mug/g.
In the invention, the water content of the positive electrode active material layer is 0-90 mug/g, and the water content of the positive electrode active material is extremely low at the moment, so that the water in the positive electrode material is not only completely eradicated to be electrolyzed in the charge-discharge process, but also completely eradicated to have side reaction with electrolyte, thereby fundamentally solving the problems of battery expansion and electric property deterioration caused by the water in the positive electrode material.
In addition, when the water content of the Prussian blue positive electrode material is extremely low, the sodium ion removing capability of the Prussian blue positive electrode material is optimal, but the stability is poor. If the capacity of completely desorbing sodium ions of the Prussian blue positive electrode material is directly used without control, the crystal structure of the Prussian blue positive electrode material collapses along with deep desorption of sodium ions in the charge and discharge process, so that the capacity of the battery is attenuated, and the cycle performance is poor. According to the Prussian blue sodium ion battery provided by the invention, the damage to the structure of the Prussian blue positive electrode material caused by the deintercalation of sodium ions in the charging and discharging process of the battery is reduced by controlling the deintercalation depth of the sodium ions in the Prussian blue positive electrode material, so that the long cycle performance of the sodium ion battery is realized under the condition that the Prussian blue positive electrode material is kept to have higher gram capacity.
Detailed description of the preferred embodiments
A preparation method of the Prussian blue sodium ion battery in the specific embodiment comprises the following steps:
firstly, manufacturing a positive plate and a negative plate, and then carrying out vacuum drying treatment on the positive plate, the negative plate and a diaphragm, so that the water content of a positive electrode active material in the positive plate is controlled to be 0-90 mu g/g, the water content of a negative electrode active material in the negative plate is controlled to be 0-200 mu g/g, and the water content of the diaphragm is controlled to be 0-200 mu g/g, wherein the method for manufacturing the positive plate and the negative plate is the same as that of a conventional sodium ion battery, and no special requirement exists;
step two, completing lamination or winding process, assembly process, liquid injection process and packaging process of the battery in a drying room environment with dew point less than-45 ℃; the specific process is the same as that of a conventional sodium ion battery, and no special requirement exists.
Further, when the battery is formed and used, the upper limit voltage and the lower limit voltage of the battery are determined according to the capacity of the unit area of the negative electrode plate of the battery, the capacity exerted by the unit area of the positive electrode plate of the battery and the area acted by the positive electrode active material voltage platform.
Further, the water content of the positive electrode active material layer was tested: the test is carried out by using a Karl Fischer moisture tester, the test temperature is 170 ℃, and the test environment is a drying room with the dew point less than-45 ℃.
Example 1
The embodiment selects Prussian blue material Na 2 Fe[Fe(CN) 6 ]And preparing a positive plate as a positive electrode material of the sodium ion battery, and then carrying out vacuum drying on the positive plate, wherein the water content of the positive electrode active material layer is finally measured to be 90 mug/g.
The sodium sheet is rolled on an aluminum foil, and the sodium itself has a water content far lower than 100 mug/g, so that the vacuum drying is not needed, and the negative plate is directly obtained after die cutting.
The negative plate, the positive plate and the diaphragm (glass fiber diaphragm) are manufactured into an electric core in a lamination mode, and then are put into a packaging shell, and are injected with liquid (NaPF is adopted 6 Electrolyte), soaking, packaging and the like to prepare the Prussian blue sodium ion battery. Then carrying out chemical formation and cyclic test on the prepared sodium ion battery, wherein the Prussian blue material Na 2 Fe[Fe(CN) 6 ]The voltage plateau that is active is the first 50% of the total discharge voltage plateau capacity.
Comparative example 1
Comparative example 1 Prussian blue type sodium ion battery was prepared in the same manner as in example 1, except that,
the obtained sodium ion battery is subjected to chemical formation and cyclic test, wherein Prussian blue material Na 2 Fe[Fe(CN) 6 ]The voltage platform that functions accounts for 100% of the total voltage platform capacity.
The charge-discharge voltage-specific capacity curve of the battery prepared in example 1 at the 1 st turn is shown in fig. 1, the charge-discharge voltage-specific capacity curve of the battery at the 2 nd turn is shown in fig. 2, and the form of the charge-discharge voltage-specific capacity curve after the 2 nd turn is similar to that of the battery at the 2 nd turn; the charge-discharge voltage-specific capacity curve of the battery obtained in comparative example 1 at the 1 st turn is shown in fig. 4, the charge-discharge voltage-specific capacity curve after the 1 st turn is similar to that of the battery obtained in the 1 st turn, and the comparative graph of the battery capacity retention curve obtained in comparative example 1 and the battery capacity retention curve obtained in example 1 is shown in fig. 3. It can be seen that the Prussian blue type sodium ion battery obtained in example 1, the capacity retention rate of 1000 cycles is 88.79%,far higher than Prussian blue material Na in comparative example 1 2 Fe[Fe(CN) 6 ]The cycle retention rate (the capacity retention rate of 37 cycles is 80%) of the conventional Prussian blue sodium ion battery obtained when the whole voltage platform fully plays a role.
At lower levels of water content (0 μg/g to 90 μg/g) of the positive electrode active material layer, although the initial capacity of the sodium ion battery is higher, if the entire sodium storage capacity of the positive electrode active material is directly utilized without control, the cycling performance of the sodium ion battery is poor and cannot be used, for example, comparative example 1. The reason is that when the water content of the positive electrode active material layer is at a low level, coordinated water in the crystal structure of the Prussian blue material is removed, and repeated deep sodium removal can cause collapse of the crystal structure of the material, so that the Prussian blue material partially loses the sodium storage capacity, and the cycling performance of the sodium ion battery is poor. In example 1, the depth of intercalation and deintercalation of sodium ions in the prussian blue positive electrode material is controlled by controlling the proportion of the whole discharge voltage platform capacity to play a role, so that the damage of deep deintercalation of sodium ions to the structure of the prussian blue positive electrode material in the charging and discharging process of the battery is weakened, and better cycle performance of the sodium ion battery is realized under the condition that the prussian blue positive electrode material is kept to have higher gram capacity.
Example 2
The Prussian blue type sodium ion battery of this example was prepared in the same manner as in example 1, except,
preparing a negative plate: and preparing the hard carbon into a negative plate, and then carrying out vacuum drying on the negative plate, so that the water content of the negative active material layer is 100 mug/g.
Preparation of a positive plate: the water content of the positive electrode active material layer was 50. Mu.g/g. As shown in FIG. 4, prussian blue material Na 2 Fe[Fe(CN) 6 ]The capability of removing and embedding sodium ions is good, and the gram capacity of the material can reach 150mAh/g; in the present embodiment, prussian blue material Na is controlled by a voltage window 2 Fe[Fe(CN) 6 ]The voltage platform which is used is the first 45% of the capacity of the whole discharge voltage platform, namely the gram capacity of the material actually used by the positive electrode material is 67.5mAh/g.
The separator used was a conventional polypropylene (PP) film.
Comparative example 2
Comparative example 2 Prussian blue type sodium ion battery was prepared in the same manner as in example 2, except that the obtained sodium ion battery was subjected to chemical formation and cyclic test, wherein Prussian blue type material Na 2 Fe[Fe(CN) 6 ]The voltage platform that functions accounts for 100% of the total voltage platform capacity.
The Prussian blue sodium ion battery prepared in example 2 has a capacity retention rate of more than 99% after 500 cycles, which is far higher than that of Prussian blue material Na in comparative example 2 2 Fe[Fe(CN) 6 ]The cycle retention rate (the capacity retention rate of 35 cycles is 80%) of the conventional Prussian blue sodium ion battery obtained when the whole voltage platform fully plays a role.
Example 3
The preparation process of the Prussian blue sodium ion battery of the embodiment is the same as that of the embodiment 2, except that,
preparation of a positive plate: the water content of the positive electrode active material layer was 20. Mu.g/g. As shown in FIG. 4, prussian blue material Na 2 Fe[Fe(CN) 6 ]The capability of removing and embedding sodium ions is good, and the gram capacity of the material can reach 150mAh/g; in the present embodiment, prussian blue material Na is controlled by a voltage window 2 Fe[Fe(CN) 6 ]The voltage platform which is used is the first 53% of the capacity of the whole charging voltage platform, namely the gram capacity of the material actually used by the positive electrode material is 80mAh/g.
Comparative example 3
The comparative example Prussian blue type sodium ion battery was prepared in the same manner as in example 2, except that,
preparation of a positive plate: the water content of the positive electrode active material layer was 100000. Mu.g/g. Because the crystal water occupies Prussian blue material Na 2 Fe[Fe(CN) 6 ]The sodium storage site of the Prussian blue material is used for reducing the real sodium storage capacity of the material 2 Fe[Fe(CN) 6 ]The gram capacity of (C) is 80mAh/g. In this comparative example, the positive electrode active material Prussian blue type material Na 2 Fe[Fe(CN) 6 ]Exert the functions ofThe applied voltage platform is 100% of the capacity of the whole charging voltage platform, namely the gram capacity of the positive electrode material is 80mAh/g.
The charge-discharge voltage-specific capacity curve of the battery obtained in example 3 at the 1 st turn is shown in fig. 5, and the form of the charge-discharge voltage-specific capacity curve after the 1 st turn is similar to that of the 1 st turn; the charge-discharge voltage-specific capacity curve of the battery obtained in comparative example 1 at the 1 st turn is shown in fig. 7, and the form of the charge-discharge voltage-specific capacity curve of the battery obtained after the 1 st turn is similar to that of the battery obtained after the 1 st turn; a graph comparing the battery capacity retention rate curve obtained in example 3 with the battery capacity retention rate curve obtained in comparative example 3 is shown in fig. 6. It can be seen that the Prussian blue sodium ion battery obtained in example 3 has a capacity retention rate of 98.19% after 70 cycles, which is far higher than that of the Prussian blue material Na in comparative example 3 2 Fe[Fe(CN) 6 ]The water content is higher, and the circulation retention rate (the circulation 70-circle capacity retention rate is 81.87%) of the conventional Prussian blue sodium ion battery is obtained when the whole voltage platform fully plays a role.
At a higher level of water content in the positive electrode active material layer, on the one hand, prussian blue type material Na is occupied by crystal water 2 Fe[Fe(CN) 6 ]The real sodium storage capacity of the material is reduced by the sodium storage sites of the material; on the other hand, water in the positive electrode active material is electrolyzed during charge and discharge, and side reactions with the electrolyte occur, resulting in battery gassing and poor cycle performance, as in comparative example 3. In embodiment 3, on one hand, the water content of the positive electrode active material layer is 20 mug/g, which not only avoids the electrolysis of water in the positive electrode material in the charge and discharge process, but also avoids the side reaction of water in the positive electrode material and electrolyte, thereby fundamentally solving the problems of battery gas expansion and electrical property deterioration caused by water in the positive electrode material; on the other hand, the deintercalation depth of sodium ions in the Prussian blue positive electrode material is controlled by controlling the proportion of the capacity of the whole discharge voltage platform, so that the damage of the deep deintercalation of the sodium ions to the structure of the Prussian blue positive electrode material in the charging and discharging process of the battery is weakened, and the better cycle performance of the sodium ion battery is realized under the condition that the Prussian blue positive electrode material is kept to have higher gram capacity.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The Prussian blue sodium ion battery comprises a positive plate and a negative plate, wherein the positive plate comprises a positive current collector and a positive active material layer which exists on the surface of the positive current collector and contains a positive active material, and the Prussian blue sodium ion battery is characterized in that: the water content of the positive electrode active material layer is 0-90 mu g/g, and the positive electrode active material only plays a part of a voltage platform in the charge and discharge process of the battery.
2. The Prussian blue type sodium ion battery according to claim 1, wherein: the positive electrode active material only plays a part of voltage platform in the charging and discharging process of the battery by carrying out capacity matching on the positive electrode plate and the negative electrode plate and controlling the upper limit voltage and the lower limit voltage of the battery in the charging and discharging process.
3. The Prussian blue type sodium ion battery according to claim 2, wherein: the formula for capacity matching of the positive plate and the negative plate is as follows: capacity per unit area of negative electrode sheet=capacity per unit area of positive electrode sheet (50% -95%) (1.0-1.5).
4. The Prussian blue type sodium ion battery according to claim 2, wherein: the partial voltage platform function means that 25% -95% of the capacity of the whole voltage platform function.
5. The Prussian blue type sodium ion battery according to claim 1, wherein: the positive electrode active material is Prussian blue material, and the molecular formula of the Prussian blue material is Na x M a [M b (CN) 6 ]Which is provided withM in (v) a Is a transition metal, M b Is a transition metal, 0<x≤2，M a Selected from one of Fe, co, mn, cu, zn, cr, V, M b One selected from Fe, co, mn, cu, zn, cr, V.
6. The Prussian blue type sodium ion battery according to claim 1, wherein: the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer which is arranged on the surface of the negative electrode current collector and contains a negative electrode active material, wherein the water content of the negative electrode active material layer is 0-200 mug/g.
7. The Prussian blue type sodium ion battery according to claim 1, wherein: the Prussian blue sodium ion battery also comprises a diaphragm, wherein the diaphragm is positioned between the positive plate and the negative plate, and the water content of the diaphragm is 0-200 mug/g.
8. A method for preparing the Prussian blue type sodium ion battery according to any one of claims 1 to 7, comprising the following steps:
firstly, manufacturing a positive plate and a negative plate, and then carrying out vacuum drying treatment on the positive plate and the negative plate to control the water content of a positive electrode active material layer in the positive plate to be 0-90 mug/g;
and step two, completing lamination or winding process, assembly process, liquid injection process and packaging process of the battery in the environment with the dew point less than-45 ℃.
9. The method of manufacturing according to claim 8, wherein: when the battery is formed and used, the upper limit voltage and the lower limit voltage of the battery are determined according to the capacity of the unit area of the negative electrode plate of the battery, the capacity of the unit area of the positive electrode plate of the battery and the area where the voltage platform of the positive electrode active material acts.
CN202111454070.0A 2021-12-01 2021-12-01 Prussian blue sodium ion battery and preparation method thereof Pending CN116207336A (en)

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Application Number Priority Date Filing Date Title
CN202111454070.0A CN116207336A (en) 2021-12-01 2021-12-01 Prussian blue sodium ion battery and preparation method thereof

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