CN117080450B - Positive pole piece of sodium ion battery and sodium ion battery - Google Patents

Positive pole piece of sodium ion battery and sodium ion battery Download PDF

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CN117080450B
CN117080450B CN202311344066.8A CN202311344066A CN117080450B CN 117080450 B CN117080450 B CN 117080450B CN 202311344066 A CN202311344066 A CN 202311344066A CN 117080450 B CN117080450 B CN 117080450B
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positive electrode
sodium ion
ion battery
additive
active material
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CN117080450A (en
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田少杰
刘凯
林雅
臧成杰
郑春龙
张艳辉
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Jiangsu Tenpower Lithium 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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 provides a positive electrode plate of a sodium ion battery and the sodium ion battery, and belongs to the technical field of sodium ion batteries.

Description

Positive pole piece of sodium ion battery and sodium ion battery
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a positive plate of a sodium ion battery and the sodium ion battery.
Background
The lithium ion battery is widely applied to the fields of mobile electronic equipment, electric automobiles, unmanned aerial vehicles and the like due to the characteristics of high energy density, long service life, no memory effect and the like. However, lithium has limited reserves on the earth, and high cost and low cost, and can restrict the long-term application of the lithium battery. The main element sodium in the sodium ion battery is abundant in the earth, and sodium carbonate which is one of the raw materials is low in price, so that the sodium ion battery is hopeful to replace the lithium ion battery in the near future. The positive electrode material of the sodium ion battery is a layered oxide material, but the layered oxide is easy to generate phase change under high temperature and high voltage, so that particles are broken, oxygen is released, metal ions are dissolved out, side reactions with electrolyte and positive and negative electrode interfaces are aggravated, and the high-temperature storage performance of the high-voltage sodium ion battery is worsened.
In chinese patent CN100433424C, it is reported that a nitrile compound may be added to a positive electrode sheet of a lithium battery, and the nitrile compound may form a metal complex with a transition metal on the positive electrode material, so as to reduce the activity of the positive electrode material, stabilize the positive electrode material, and complex metal ions eluted from the positive electrode material, thereby inhibiting the damage to the negative electrode interface.
Disclosure of Invention
However, the inventor researches that, as the alkalinity of the positive electrode material of the sodium ion battery is very high, the nitrile compound is decomposed and deactivated, and in addition, the nitrile compound has higher solubility in the electrolyte, on one hand, the conductivity of the electrolyte is reduced, on the other hand, the nitrile compound migrates to the negative electrode interface to generate a reduction side reaction, and on the contrary, the performance of the sodium ion battery is deteriorated.
In addition, the strong alkali in the positive electrode material not only can cause decomposition reaction between the electrolyte and the surface of the positive electrode material, but also can cause the positive electrode slurry to generate gel, thereby influencing the processing performance.
In view of the above-mentioned shortcomings found by the inventors, an object of the present invention is to provide a positive electrode sheet of a sodium ion battery and a sodium ion battery, which can improve the processing performance of the positive electrode of the sodium ion battery and the high-temperature storage life of the sodium ion battery.
To achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a positive electrode plate of a sodium ion battery, which comprises a positive electrode active material layer and a positive electrode current collector, wherein the positive electrode active material layer is positioned on one side or two sides of the current collector, the positive electrode active material layer comprises a positive electrode active material, a conductive agent, a binder and an additive A, and the additive A is a cyano carboxylic acid compound.
Preferably, the additive A is at least one of cyanoacetic acid, 3-cyanopropionic acid, 4-cyanobutyric acid, 5-cyanovaleric acid, 6-cyanohexanoic acid, 7-cyanoheptanoic acid, p-cyanobenzoic acid and compounds represented by the following formulas I-1 to I-6:
。
preferably, the additive a is contained in an amount of 0.1% to 2%, for example, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8% or 2%, based on 100% by weight of the total of the positive electrode active material, the conductive agent, the binder and the additive a in the positive electrode active material layer.
Preferably, the positive electrode active material is a layered oxide having a structural formula of NaM x O y M is selected from one or a combination of at least two of iron, copper, nickel, cobalt or manganese, x is more than or equal to 0.8 and less than or equal to 1.5, y is more than or equal to 1.5 and less than or equal to 2.5, and the values of x and y meet the charge balance of a chemical formula.
Preferably, the positive electrode active material is NaFe 0.5 Mn 0.5 O 2 、NaNi 0.3 Fe 0.4 Mn 0.3 O 2 、NaNi 0.33 Fe 0.34 Mn 0.33 O 2 、NaNi 0.25 Fe 0.5 Mn 0.25 O 2 、NaNi 0.2 Cu 0.1 Fe 0.4 Mn 0.3 O 2 、NaNi 0.25 Fe 0.4 Co 0.1 Mn 0.25 O 2 、NaNi 0.5 Fe 0.4 Mn 0.4 O 2.4 Or NaNi 0.4 Fe 0.2 Mn 0.3 O 1.8 Any one or a combination of at least two of the foregoing.
Preferably, the conductive agent includes any one or a combination of at least two of carbon black, carbon nanotubes, graphene, conductive graphite, or carbon fibers.
Preferably, the conductive agent includes at least one of carbon black, carbon nanotubes, and graphene.
Preferably, the positive electrode current collector is selected from aluminum foil, aluminum foil doped with other elements, or aluminum foil with a coating layer on the surface.
In a second aspect, the invention provides a sodium ion battery, comprising the positive electrode plate, the negative electrode plate, the isolating film and the electrolyte of the sodium ion battery.
Preferably, the negative electrode material in the negative electrode sheet comprises hard carbon and/or soft carbon.
Preferably, the electrolyte comprises a solvent, an electrolyte salt and an additive.
Preferably, the solvent in the electrolyte solution contains any one or a combination of at least two of carbonate solvents, fluorocarbonate solvents, carboxylate solvents, fluorocarboxylate solvents, ether solvents, or fluoroether solvents.
Preferably, the carbonate solvent is any one or a combination of at least two of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate or methyl propyl carbonate.
Preferably, the fluorocarbonate solvent is any one or a combination of at least two of fluoroethylene carbonate, difluoroethylene carbonate, methyltrifluoromethyl carbonate, methyltrifluoroethyl carbonate or bis (2, 2-trifluoroethyl) carbonate.
Preferably, the carboxylic acid ester solvent is any one or a combination of at least two of methyl formate, methyl acetate, methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate, propyl propionate or ethyl butyrate.
Preferably, the fluorocarboxylate solvent is any one or a combination of at least two of ethyl fluoroacetate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, 2-trifluoroethyl difluoroacetate, methyl pentafluoropropionate or 2, 2-difluoroethyl acetate.
Preferably, the ether solvent is any one or a combination of at least two of tetrahydrofuran, 1, 3-dioxane, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Preferably, the method comprises the steps of, the fluoroether solvent is bis (2, 2-trifluoroethyl) ether 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether or 1, 2-tetrafluoroethyl-any one or a combination of at least two of 2, 3-tetrafluoropropyl ether.
Preferably, the additive in the electrolyte comprises any one or a combination of at least two of carbonate additives, nitrile additives, sulfur-containing element additives, fluorine-containing element additives, boron-containing element additives or phosphorus-containing element additives.
Preferably, the electrolyte additive is any one or a combination of at least two of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, succinonitrile, adiponitrile, ethylene glycol bis (propionitrile) ether, 1, 4-dicyano-2-butene, 1,2, 3-tris (2-cyanooxy) propane, 1,3, 6-hexanetrinitrile, 1, 3-propane sultone, 1, 3-propenolactone, ethylene sulfite, ethylene sulfate, 4-fluoroethylene sulfate, propylene sulfate, sodium difluorooxalato borate, tris (trimethylsilane) phosphate or tris (trimethylsilane) phosphite.
Preferably, the electrolyte salt is selected from the group consisting of NaPF 6 、NaFSI、NaTFSI、NaBF 4 、NaClO 4 、NaAsF 6 Or NaSbF 6 Any one or a combination of at least two of these.
Compared with the prior art, the invention has the beneficial effects that:
according to the scheme provided by the invention, the additive A cyano carboxylic acid compound in the positive electrode plate of the sodium ion battery contains carboxyl, can be combined with strong alkali in the positive electrode material, inhibits gel generation in slurry, so that the processing performance is improved, and the additive A cyano carboxylic acid compound, sodium hydroxide and sodium carbonate on the surface of the positive electrode produce water, carbon dioxide and sodium cyano carboxylate, wherein the water and the carbon dioxide volatilize from the positive electrode active layer in the preparation process of the positive electrode plate, and the generated sodium cyano carboxylate has a higher boiling point and is remained on the surface of the positive electrode material as a part of an interfacial film.
In addition, compared with the method that nitrile compounds are added into the positive electrode plate, the additive A cyano carboxylic acid compound is preferentially formed by the reaction of carboxyl and alkali, so that cyano is not decomposed by strong alkali, the solubility of a cyano-generated product sodium cyano-carboxylate in electrolyte is relatively low, a large amount of cyano-generated product sodium cyano-carboxylate is not dissolved into the electrolyte to cause the reduction of the conductivity of the electrolyte, and the cyano-generated product sodium cyano-carboxylate does not run to a negative electrode to deteriorate a negative electrode interface.
The product sodium cyano carboxylate of the additive A cyano carboxylic acid compound forms an anchoring group on the surface of the positive electrode in a carboxyl form through chemical reaction, so that the sodium cyano carboxylate well fixes the surface of the positive electrode to form a positive electrode interface film to inhibit side reaction on the surface of the positive electrode, and the cyano group with a carbon chain on the other head can complex metal ions dissolved out of the positive electrode material and inhibit migration of the metal ions to the electrolyte and the surface of the negative electrode to generate destructive action, so that the oxidizing property of the surface of the positive electrode can be reduced while the surface of the positive electrode is stabilized, and finally the processability and high-temperature storage performance of sodium ions can be improved.
Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments in combination with or instead of the features of the other embodiments.
It should be emphasized that the term "comprises/comprising" when used herein is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps or components.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the embodiment of the invention, the additive materials used in the preparation of the positive electrode sheet are as follows:
additive A: 3-cyanopropionic acid, 5-cyanovaleric acid, p-cyanobenzoic acid;
contrast additive: n-capronitrile.
Preparation of sodium ion battery:
preparation of positive electrode sheet
The positive electrode plate is prepared according to the following preparation methods in sequence in each of the embodiments 1 to 5:
positive electrode material sodium nickel iron manganese oxide NaNi 0.3 Fe 0.4 Mn 0.3 O 2 The mass ratio of the binder (polyvinylidene fluoride) to the conductive agent (conductive carbon black) is fixed to 96:2:2, and the total weight of the positive electrode active material, the conductive agent, the binder and the additive A in the positive electrode active material layer is taken as 100%, and the content of the sum of the mass of the positive electrode material sodium ferronickel manganate, the binder and the conductive agent is shown in table 1.
Table 1: the positive electrode sheet of examples 1 to 5 comprises the components and the contents
Mixing anode material sodium nickel iron manganese oxide, a binder, a conductive agent and an additive A according to the respective proportion requirements, adding N-methyl pyrrolidone (NMP), and stirring to prepare anode slurry, wherein the NMP content in the anode slurry is 25wt%, and the anode slurry needs to be reserved for viscosity test.
And uniformly coating the anode slurry on an aluminum foil, airing the coated aluminum foil at room temperature, transferring to a 120 ℃ oven for drying for 1h, then drying at 85 ℃ for cold pressing, trimming, cutting pieces and slitting, drying at 100 ℃ for 4h under vacuum condition, and welding tab to prepare the anode sheet of the sodium ion secondary battery meeting the requirements.
According to comparative examples 1-3, positive pole pieces are prepared sequentially according to the preparation method in the embodiment:
positive electrode material sodium nickel iron manganese oxide NaNi 0.3 Fe 0.4 Mn 0.3 O 2 The mass ratio of the binder (polyvinylidene fluoride) to the conductive agent (conductive carbon black) is fixed to 96:2:2, the total weight of the positive electrode active material, the conductive agent, the binder and the additive A in the positive electrode active material layer is taken as 100%, the content of the sum of the positive electrode material, the sodium ferronickel manganate, the binder and the conductive agent is shown in table 2, and the type and the content of the additive A and the content of the comparative additive n-capronitrile are shown in the table 2.
Table 2: composition and content of each component of the positive electrode sheet in comparative examples 1 to 3
The specific process of the positive pole piece of the comparative example is the same as that of the example, the preparation process of the positive pole piece of the reference example is used for preparation, and the positive pole slurry is required to be reserved for viscosity test.
(II) preparation of electrolyte
Firstly, in a glove box, slowly adding sodium hexafluorophosphate into a mixed solution of solvent Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), and after the temperature in a container is reduced to room temperature, adding 1% fluoroethylene carbonate (FEC) additive. The mass ratio of EC, DMC and EMC in the electrolyte is EC: DMC: emc=1:1:1, the molar concentration of sodium hexafluorophosphate in the electrolyte is 1mol/L.
(III) preparation of negative electrode sheet
Dissolving hard carbon, a thickener sodium carboxymethyl cellulose (CMC), a binder styrene-butadiene rubber emulsion (SBR) and a conductive agent (conductive carbon black) in solvent deionized water according to a mass ratio of 94:1:2:3, and uniformly mixing to prepare negative electrode slurry;
and uniformly coating the negative electrode slurry on a current collector copper foil, drying at 85 ℃ for cold pressing, trimming, cutting and splitting, drying at 110 ℃ for 4 hours under vacuum, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion secondary battery meeting the requirements.
Preparation of sodium ion cell
And winding the corresponding positive plate, negative plate and isolating film (PE film+3um ceramic coating) into a bare cell, then filling the bare cell into an aluminum plastic film, baking at 90 ℃ to remove water, filling electrolyte, sealing, and performing the procedures of standing, hot cold pressing, formation, exhaust, capacity division and the like to obtain the sodium ion battery.
The positive electrode slurry and the sodium ion battery obtained above are tested, including the following performance tests:
positive electrode slurry viscosity test
At 25 ℃, a portion of the slurry from the positive electrode shipment of the different groups was taken out and left to stand for 24 hours, and the viscosity of the slurry was tested and recorded.
Sodium ion battery 60 ℃ high temperature storage test
Firstly, standing the sodium ion battery at 25 ℃ for 30 minutes; charging to 4.05V at a constant current of 0.5C, further charging to a current of 0.5C at a constant voltage of 4.05V; then, the sodium ion battery was discharged at a constant current of 0.5C for 1.5V, at which time the discharge capacity was recorded as C 0s The method comprises the steps of carrying out a first treatment on the surface of the Charging to 4.05V with constant current of 0.5C, further charging to 0.5C with constant voltage of 4.05V, and recording that the voltage of sodium ion battery is V 0 。
Then the sodium ion battery is stored for 30 days at 60 ℃, after the storage is finished, the full charge voltage of the sodium ion battery at the moment is tested and is recorded as V 30 . Then placing the sodium ion secondary battery in an environment of 25 ℃, and discharging the sodium ion battery by 1.5V at a constant current of 0.5 ℃; then charging the sodium ion secondary battery to 4.05V with a constant current of 0.5C, and further charging the sodium ion secondary battery to 0.5C with a constant voltage of 4.05V; then, the sodium ion secondary battery was discharged to 1.5V with a constant current of 0.5C, at which time the discharge capacity was noted as C 30s 。
In addition, after all the sodium ion batteries are tested, the battery cells are disassembled, the negative electrode plate is taken out, the negative electrode active material layer is scraped, strong acid is used for digestion, solution is prepared after filtration, the obtained solution is tested by ICP, the content of iron, nickel and manganese in the obtained solution is recorded, and the sum of the content of iron, nickel and manganese in the negative electrode active material obtained by ICP test is the sum of the deposition amount of negative electrode metal ions.
Storage capacity recovery rate (%) =c after 30 days of sodium ion storage 30S /C 0S ；
Self-discharge rate (mV/d) = (V) after sodium ion storage for 30 days 0 -V 30 )/30。
The performance test data of the sodium ion batteries of the inventive examples and comparative examples are shown in table 3.
Table 3: test results of sodium ion cell
From comparative examples 1 to 2 and examples 1 to 3 in table 3, it can be seen that the viscosity, the storage capacity recovery at 60 ℃ and the self-discharge rate and the deposition of negative metal ions after 24 hours of standing of the positive electrode slurry are significantly improved after adding the additive a to the positive electrode sheet of the sodium ion battery, compared with the positive electrode sheet without adding the additive a. The additive A can neutralize residual alkali in the positive electrode, and obviously improves the viscosity and gel phenomenon after 24 hours of standing, thereby improving the processing performance of the positive electrode plate; the additive A can complex transition metal ions dissolved out from the positive electrode to the surface, obviously reduce the deposition of the transition metal ions on the negative electrode, can be anchored at the interface of the positive electrode through carboxyl functional groups to serve as an interface film, and can stabilize the positive electrode to reduce the oxidation activity of the surface of the positive electrode, so that the high-temperature storage capacity and self-discharge are improved. However, when the additive a is excessively used, the pH in the positive electrode slurry is lowered too low, carboxylic acid groups on the excessive additive a are agglomerated together with other materials of the positive electrode through hydrogen bonding, the viscosity of the slurry may rise instead, and too high acidity may damage the positive electrode surface and cause decomposition of electrolyte components, thereby deteriorating storage capacity recovery at 60 ℃ and self-discharge rate deterioration, so that the content of the additive a must be controlled within a certain range.
It can be seen from examples 2 and 4 to 5 in Table 3 that different kinds and contents of the additive A can be used to obtain different improvements. The additive A contains carboxylic acid groups, and the number of the carboxylic acid groups is 1, and the acidity is close, so that the additive A is added into the positive electrode, and the viscosity improvement result of the positive electrode slurry is close.
From table 3, it can be seen from comparative example 3 and example 4 that the positive electrode slurry of 5-cyanovaleric acid in additive a had better viscosity after 24 hours standing, storage capacity recovery at 60 ℃, self-discharge rate after storage at 60 ℃ and improvement effect of negative electrode metal ion deposition than the positive electrode slurry of comparative additive n-capronitrile, and in particular, the viscosity after 24 hours standing of the positive electrode slurry was not improved. Although 5-cyanovaleric acid and n-capronitrile contain the same carbon number and 1 cyano functional group, the latter has no carboxylic acid functional group, and the alkali in the positive electrode cannot be neutralized, so that the viscosity of the positive electrode slurry after 24 hours of standing cannot be improved, side reaction on the surface of the positive electrode, decomposition of electrolyte and partial decomposition of n-capronitrile caused by the alkali cannot be improved, in addition, the n-capronitrile cannot form carboxylate to improve the boiling point like the additive A, and part of the carboxylate volatilizes in the baking process of the positive electrode sheet, so that the protection of the positive electrode is greatly reduced, and various performances are not as good as those of the additive A.
Any numerical value recited herein includes all values of the lower and upper values that are incremented by one unit from the lower value to the upper value, as long as there is a separation of at least two units between any lower value and any higher value. For example, if it is stated that the number of components or the value of a process variable (e.g., temperature, pressure, time, etc.) is from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, then the purpose is to explicitly list such values as 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc. in this specification as well. For values less than 1, one unit is suitably considered to be 0.0001, 0.001, 0.01, 0.1. These are merely examples that are intended to be explicitly recited in this description, and all possible combinations of values recited between the lowest value and the highest value are believed to be explicitly stated in the description in a similar manner.
Unless otherwise indicated, all ranges include endpoints and all numbers between endpoints. "about" or "approximately" as used with a range is applicable to both endpoints of the range. Thus, "about 20 to 30" is intended to cover "about 20 to about 30," including at least the indicated endpoints.
All articles and references, including patent applications and publications, disclosed herein are incorporated by reference for all purposes. The term "consisting essentially of …" describing a combination shall include the identified element, ingredient, component or step as well as other elements, ingredients, components or steps that do not substantially affect the essential novel features of the combination. The use of the terms "comprises" or "comprising" to describe combinations of elements, components, or steps herein also contemplates embodiments consisting essentially of such elements, components, or steps. By using the term "may" herein, it is intended that any attribute described as "may" be included is optional.
Multiple elements, components, parts or steps can be provided by a single integrated element, component, part or step. Alternatively, a single integrated element, component, part or step may be divided into separate plural elements, components, parts or steps. The disclosure of "a" or "an" to describe an element, component, section or step is not intended to exclude other elements, components, sections or steps.
It should be understood that many embodiments and many applications other than the examples provided will be apparent to those skilled in the art upon reading the above description. The scope of the present teachings should, therefore, be determined not with reference to the above description, but instead should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated herein by reference for the purpose of completeness. The omission of any aspect of the subject matter disclosed herein in the preceding claims is not intended to forego such subject matter, nor should the inventors regard such subject matter as not be considered to be part of the disclosed subject matter.

Claims (8)

1. The positive pole piece of the sodium ion battery is characterized by comprising: a positive electrode active material layer and a positive electrode current collector;
the positive electrode active material layer is positioned on one side or two sides of the positive electrode current collector, and comprises a positive electrode active material, a conductive agent, a binder and an additive A, wherein the additive A is a cyano carboxylic acid compound;
the total weight of the positive electrode active material, the conductive agent, the binder and the additive A in the positive electrode active material layer is calculated as 100%, and the content of the additive A is 0.1% -2%;
the positive electrode active material is a layered oxide, and has a structural formula of NaM x O y M is selected from one or a combination of at least two of iron, copper, nickel, cobalt or manganese, x is more than or equal to 0.8 and less than or equal to 1.5, and y is more than or equal to 1.5 and less than or equal to 2And 5, the values of x and y meet the chemical formula charge balance.
2. The positive electrode sheet of sodium ion battery according to claim 1, wherein the additive a is at least one of cyanoacetic acid, 3-cyanopropionic acid, 4-cyanobutyric acid, 5-cyanovaleric acid, 6-cyanohexanoic acid, 7-cyanoheptanoic acid, p-cyanobenzoic acid, and compounds represented by the following formulas i-1 to i-6:
。
3. the positive electrode sheet of sodium ion battery according to claim 1, wherein the positive electrode active material is NaFe 0.5 Mn 0.5 O 2 、NaNi 0.3 Fe 0.4 Mn 0.3 O 2 、NaNi 0.33 Fe 0.34 Mn 0.33 O 2 、NaNi 0.25 Fe 0.5 Mn 0.25 O 2 、NaNi 0.2 Cu 0.1 Fe 0.4 Mn 0.3 O 2 、NaNi 0.25 Fe 0.4 Co 0.1 Mn 0.25 O 2 、NaNi 0.5 Fe 0.4 Mn 0.4 O 2.4 Or NaNi 0.4 Fe 0.2 Mn 0.3 O 1.8 Any one or a combination of at least two of the foregoing.
4. The positive electrode sheet of a sodium ion battery according to claim 1, wherein the conductive agent comprises any one or more of carbon black, carbon nanotubes, graphene, conductive graphite, carbon fibers.
5. The positive electrode sheet of a sodium ion battery according to claim 1, wherein the positive electrode current collector is selected from aluminum foil or aluminum foil containing doping of other elements or aluminum foil containing a coating layer on the surface.
6. A sodium ion battery, wherein the sodium ion battery comprises: the positive electrode sheet, negative electrode sheet, separator and electrolyte of sodium ion battery as claimed in any one of claims 1 to 5.
7. The sodium ion battery of claim 6, wherein the negative electrode material in the negative electrode tab comprises hard carbon and/or soft carbon.
8. The sodium ion battery of claim 6, wherein the electrolyte comprises: solvents, electrolyte salts and additives;
the additive in the electrolyte comprises at least one of a carbonate additive, a nitrile additive, a sulfur-containing element additive, a fluorine-containing element additive, a boron-containing element additive or a phosphorus-containing element additive.
CN202311344066.8A 2023-10-17 2023-10-17 Positive pole piece of sodium ion battery and sodium ion battery Active CN117080450B (en)

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