CN116230892A - Modified O3 type sodium ion battery layered oxide positive electrode material and preparation method and application thereof - Google Patents

Modified O3 type sodium ion battery layered oxide positive electrode material and preparation method and application thereof Download PDF

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CN116230892A
CN116230892A CN202310163721.3A CN202310163721A CN116230892A CN 116230892 A CN116230892 A CN 116230892A CN 202310163721 A CN202310163721 A CN 202310163721A CN 116230892 A CN116230892 A CN 116230892A
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positive electrode
sodium
modified
nani
ion battery
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王迪
董英男
张继宗
蒋绮雯
司煜
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Jiangsu Zenio New Energy Battery Technologies Co Ltd
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Jiangsu Zenio New Energy Battery Technologies 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 a modified O3 type sodium ion battery layered oxide positive electrode material, a preparation method and application thereof, wherein the positive electrode material comprises A x BS y @NaNi a Fe b Mn c O 2 From A x BS y With NaNi a Fe b Mn c O 2 Mixing and sintering to obtain; wherein A is at least one of alkali metal element, transition metal element and In, bi, pb, gaB is at least one of P, si, C, N, sb, se, ge, te, sn, x and y are more than or equal to 1,0 is less than or equal to a, B and c are less than or equal to 1, and a+b+c=1. The invention prepares A by a one-step sintering method x BS y Coating modified O3 type sodium ion battery layered oxide positive electrode material A x BS y The contact area between the layered oxide and the electrolyte is reduced by the cladding, the occurrence of side reaction between the layered oxide and the electrolyte is effectively reduced, and the cycle performance of the full battery composed of the modified O3 phase layered oxide material is optimized; in addition A x BS y The existence of the catalyst is favorable for the rapid migration of sodium ions in the anode material, and the capacity of the battery is effectively improved. In addition, when A is an alkali metal element, A x BS y The doping of the (C) also supplements alkali metal for the anode material, and plays a role in pre-alkali metallization.

Description

Modified O3 type sodium ion battery layered oxide positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a modified O3 type sodium ion battery layered oxide positive electrode material, a preparation method and application thereof.
Background
Among various positive electrode materials of sodium ion batteries, O3-phase layered oxides are receiving attention because of their advantages of providing sufficient sodium in a full battery, high electrochemical activity, high theoretical specific capacity, and ease of synthesis. However, the problems of low specific capacity, poor cycle performance, etc. limit the practical application of the O3-phase layered oxide.
Therefore, how to improve the specific capacity, the ion diffusion rate and the structural stability of the O3 type sodium ion battery layered anode material and improve the cycling performance of the sodium ion battery becomes one of the key problems in the sodium ion battery related technology.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modified O3 type sodium ion battery layered oxide positive electrode material, a preparation method and application thereof, wherein A stably existing in the air is prepared by a solid phase sintering method x BS y Coating and modifying the O3 phase layered oxide anode material, and passing through A x BS y The modified O3 phase layered oxide material shows high specific discharge capacity and excellent cycle performance in a full cell.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention provides a modified O3 type sodium ion battery layered oxide positive electrode material, which comprises A x BS y @NaNi a Fe b Mn c O 2 I.e. A x BS y Coated NaNi a Fe b Mn c O 2 A positive electrode material; wherein A is selected from one or more of alkali metal element, transition metal element and In, bi, pb, ga, B is selected from one or more of P, si, C, N, sb, se, ge, te, sn, x and y are larger than or equal to 1,0 is smaller than or equal to a, B and c are smaller than or equal to 1, and a+b+c=1.
Further, the alkali metal element is preferably Li, na; the transition metal element is preferably Mn, ni, cu, fe.
Further, the A x BS y Comprises Li 2 SiS 3 、Li 4 SiS 4 、MnPS 3 、NiPS 3 、Cu 3 SbS 3 、In 2 PS 3 、Bi 4 TeS 13 、Pb 2 SnS 2 、GaPS 4 、Fe 3 SiS 2 At least one of them.
Further, the A x BS y Comprises Li 2 SiS 3 And a=0.34, b=c=0.33.
Further, the A x BS y @NaNi a Fe b Mn c O 2 The particle diameter D50 of the particles is 0.01-58.27 mu m, and the specific surface area is 0.01-33.68 m 2 Per gram, the water content is 0.01 to 1.58 percent.
Further, the A x BS y @NaNi a Fe b Mn c O 2 Is A x BS y Coated NaNi a Fe b Mn c O 2 And a positive electrode material.
The second aspect of the invention provides a preparation method of the modified O3 type sodium ion battery layered oxide positive electrode material, which comprises the steps of A x BS y With NaNi a Fe b Mn c O 2 The mixture is evenly mixed and the mixture is stirred,solid phase sintering to obtain the A x BS y @NaNi a Fe b Mn c O 2 。
Further, will A x BS y With NaNi a Fe b Mn c O 2 The mixture is ground and mixed uniformly.
Further, the A x BS y With NaNi a Fe b Mn c O 2 The feeding molar ratio of (2) is 0.01-0.1:1.
Further, in the step of solid phase sintering: the temperature rising rate is 10-30 ℃/min, and the sintering temperature is 300-800 ℃.
Further, the A x BS y The preparation of (2) comprises:
impregnating metal A powder with A-containing x S y Obtaining a mixed solution in the organic solvent of (2);
will contain BCl z Adding the organic solvent into the mixed solution, and obtaining A through reaction x BS y 。
Further, the organic solvent is selected from one or more of methanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, isopropyl acetate, dimethylformamide, propylene glycol, pyridine and diethyl ether.
Further, the metal A powder is impregnated with a powder containing A x S y In the organic solvent of (2), the polysulfide layer is formed on the surface of the metal A powder by centrifugal stirring for 4 to 16 hours.
Further, the preparation of the mixed solution is carried out under the condition that the water oxygen value is less than or equal to 0.1 ppm.
Further, the BCl z Is B chloride.
Further, it will contain BCl z Adding the organic solvent into the mixed solution, and then centrifugally shaking for 10-25 min to perform reaction. BCl (binary coded decimal) z And A is a 2 S x And A metal to form a thermodynamically stable ACl product and A x BS y Wherein the byproduct ACl can be dissolved in an organic solvent to obtain a target product A x BS y 。
Advancing oneStep by step, the NaNi a Fe b Mn c O 2 The preparation of (2) comprises: will prepare the NaNi a Fe b Mn c O 2 Mixing the metal salts according to a proportion, heating to 800-1200 ℃ at a heating rate of 0.01-10 ℃/min, and preserving heat for 0.5-48 h to obtain the NaNi a Fe b Mn c O 2 。
Further, the metal salt comprises sodium salt and NaNi a Fe b Mn c O 2 Or comprises sodium salt and precursor metal salt, wherein the metal element in the precursor metal salt is NaNi a Fe b Mn c O 2 Other metal elements than sodium.
Further, the sodium salt is one or more of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate.
Further, the metal salts of the other metal elements include one or more of nickel-containing salts, iron-containing salts, and manganese-containing salts.
Further, the nickel-containing salt is one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide, nickel carbonyl and nickel oxide.
Further, the iron-containing salt is one or more of ferric oxide, ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate.
Further, the manganese-containing salt is one or more of potassium permanganate, potassium manganate and manganese oxide.
Further, the precursor metal salt is one or more of nickel oxide, nickel iron manganese oxide, iron oxide, manganese iron oxide, nickel manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron manganese hydroxide and nickel manganese hydroxide.
Further, metal salts are prepared according to the NaNi a Fe b Mn c O 2 The molar ratio of each metal element is weighed, wherein the sodium salt content is slightly largerIn the required molar amount to compensate for the loss of sodium content during sintering. For example, when the positive electrode material is NaNi 0.34 Fe 0.33 Mn 0.33 O 2 When the metal salt is selected from sodium hydroxide, nickel oxide, ferrous oxide and manganese oxide, the molar ratio of the sodium hydroxide, the nickel oxide, the ferrous oxide and the manganese oxide is preferably 1-1.1:0.34:0.33:0.33.
The third aspect of the invention provides a positive electrode plate, which comprises the modified O3 type sodium ion battery layered oxide positive electrode material of the first aspect and/or the modified O3 type sodium ion battery layered oxide positive electrode material prepared by the preparation method of the second aspect.
The fourth aspect of the invention provides a sodium ion pool, which comprises the positive pole piece of the third aspect.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a modified O3 type sodium ion battery layered oxide anode material, which is characterized in that A which exists in air stably x BS y Coating and modifying O3 phase layered oxide material by solid phase sintering method, and passing through A x BS y The coating-modified O3-phase layered oxide material exhibits high specific discharge capacity and excellent cycle performance in a full cell, presumably due to a x BS y The coating of the electrolyte reduces the contact area between the O3 phase layered oxide and the electrolyte, reduces the side reaction between the O3 phase layered oxide and the electrolyte, and simultaneously comprises A in the positive electrode material x BS y Provides a good migration channel for sodium ions, thereby effectively optimizing the cycle performance and specific capacity of the modified cathode material in the full battery.
2. The invention adopts the modified material A containing alkali metal elements x BS y Coating modification is carried out on the O3 type sodium ion battery layered oxide positive electrode material, and the modified O3 phase layered oxide positive electrode material contains alkali metal elements, so that alkali metal can be supplemented for the positive electrode material, the effect of pre-alkali metallization is achieved, and the loss of initial capacity of the battery is effectively compensated.
3. The modified O3 type sodium ion battery layered oxide anode material provided by the invention has the advantages of simple preparation method, easiness in operation and capability of being prepared in a large scale; the full battery prepared by taking the full battery as the positive electrode material and hard carbon as the negative electrode material can realize the initial specific capacity of 140.5mA h/g in a voltage interval of 2-4V, the initial coulomb efficiency is 86.1%, the capacity retention rate is 85.9% after 1000 circles of circulation, and the full battery has excellent battery capacity and circulation stability.
Drawings
FIG. 1 is a test flow chart of ICP-OES;
FIG. 2 shows the NaNi prepared in example 1 0.34 Fe 0.33 Mn 0.33 O 2 ICP test result diagram of powder (NNFM-1);
FIG. 3 is Li prepared in example 1 2 SiS 3 SEM images of the material (a) and TEM images of the material (b);
FIG. 4 is Li prepared in example 1 2 SiS 3 A transmission Mapping graph of the material;
FIG. 5 is Li prepared in example 1 2 SiS 3 X-ray diffraction pattern of @ NNFM-1 material;
FIG. 6 is Li prepared in example 1 2 SiS 3 X-ray photoelectron spectrum of @ NNFM-1 material.
Detailed Description
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. The term "comprising" or "comprises" as used herein means that it may include or comprise other components in addition to the components described. The term "comprising" or "comprising" as used herein may also be replaced by "being" or "consisting of" closed.
As described in the background art, the problems of low specific capacity, poor cycle performance, and the like are one of the main reasons that limit the practical application of sodium ion batteries. The low diffusion rate of ions in the positive electrode material can lead to low specific capacity of the battery, and side reactions of the positive electrode material and electrolyte can influence the cycle performance in the cycle process. The problems of the conventional methods such as doping and coating of elements cannot be well improved for the positive electrode material, and particularly in sodium ion batteries using hard carbon as the negative electrode material.
To solve the above technical problems, an embodiment of the present invention provides a modified O3 type sodium ion battery layered oxide cathode material, comprising a x BS y @NaNi a Fe b Mn c O 2 I.e. A x BS y Coated NaNi a Fe b Mn c O 2 A positive electrode material; wherein A is selected from one or more of alkali metal element, transition metal element and In, bi, pb, ga, B is selected from one or more of P, si, C, N, sb, se, ge, te, sn, x and y are larger than or equal to 1,0 is smaller than or equal to a, B and c are smaller than or equal to 1, and a+b+c=1.
The invention leads A with good stability in air x BS y Coating the O3 phase layered oxide material to obtain a modified positive electrode material, and carrying out A treatment x BS y The coating modified positive electrode material reduces the contact area between the O3 phase layered oxide and the electrolyte, reduces the side reaction between the O3 phase layered oxide and the electrolyte, and enables the full battery containing the modified positive electrode material to show excellent cycle performance; in addition, A x BS y The coating layer provides a migration channel for migration of sodium ions in the positive electrode material, and can accelerate the migration rate of sodium ions in the positive electrode material, so that the problem of low specific capacity of the O3 phase layered oxide positive electrode material in a full battery is effectively solved.
In some preferred embodiments, the alkali metal element is preferably Li, na; the transition metal element is preferably Mn, ni, cu, fe; more preferably, the A x BS y Comprises Li 2 SiS 3 、Li 4 SiS 4 、MnPS 3 、NiPS 3 、Cu 3 SbS 3 、In 2 PS 3 、Bi 4 TeS 13 、Pb 2 SnS 2 、GaPS 4 、Fe 3 SiS 2 At least one of them.
It is preferable that a is an alkali metal element. When A is x BS y When alkali metal element is contained, the catalyst is prepared through A x BS y The O3 phase layered oxide after coating modification treatment contains alkali metal element A, can supplement alkali metal for the positive electrode material, plays a role of pre-alkali metallization, and can effectively compensate the loss of initial capacity of the battery. For example, said A x BS y Is Li 2 SiS 3 And a=0.34, b=c=0.33, the presence of li can supplement the positive electrode material with alkali metal, thereby functioning as pre-alkali metallization.
In some preferred embodiments, the A x BS y @NaNi a Fe b Mn c O 2 The particle diameter D50 of the particles is 0.01-58.27 mu m, and the specific surface area is 0.01-33.68 m 2 Per gram, the water content is 0.01 to 1.58 percent.
The embodiment of the invention also provides a preparation method of the modified O3 type sodium ion battery layered oxide positive electrode material, which comprises the following steps of A x BS y With NaNi a Fe b Mn c O 2 Uniformly mixing, and obtaining the A through solid phase sintering x BS y @NaNi a Fe b Mn c O 2 。
In some preferred embodiments, A will be x BS y With NaNi a Fe b Mn c O 2 The mixture is ground and mixed uniformly. Grinding A x BS y Crushing the material into small particle powder structure to make it and NaNi a Fe b Mn c O 2 Can be uniformly mixed, and further obtain A with stable structure and performance through solid phase sintering x BS y @NaNi a Fe b Mn c O 2 。
In some preferred embodiments, the A x BS y With NaNi a Fe b Mn c O 2 The feeding molar ratio of (2) is 0.01-0.1:1. Will A x BS y With NaNi a Fe b Mn c O 2 In a proper amountMixing the molar ratios, and obtaining A by solid phase sintering x BS y The coated O3 phase layered oxide positive electrode material improves the cycle performance and specific capacity of the battery on the premise of not influencing the energy density of the battery.
In some preferred embodiments, the step of solid phase sintering comprises: the temperature rising rate is 10-30 ℃/min, the sintering temperature is 300-800 ℃, and the temperature rises to 650 ℃ at the temperature rising rate of 30 ℃/min.
In some preferred embodiments, the A x BS y The preparation of (2) comprises:
impregnating metal A powder with A-containing x S y Obtaining a mixed solution in the organic solvent of (2);
will contain BCl z Adding the organic solvent into the mixed solution, and obtaining A through reaction x BS y 。
Wherein BCl z Chlorides of B, e.g. SiCl 4 The method comprises the steps of carrying out a first treatment on the surface of the The organic solvent is preferably one or more of methanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, isopropyl acetate, dimethylformamide, propylene glycol, pyridine and diethyl ether.
In some preferred embodiments, metal A powder is impregnated with a composition containing A x S y In the organic solvent of (2), the polysulfide layer is formed on the surface of the metal A powder by centrifugal stirring for 4 to 16 hours.
In some preferred embodiments, the preparation of the mixed solution is performed at a water oxygen value of 0.1ppm or less.
In some preferred embodiments, will contain BCl z Adding the organic solvent into the mixed solution, and then centrifugally shaking for 10-25 min to perform reaction. BCl (binary coded decimal) z And A is a 2 S x And A metal to form a thermodynamically stable ACl product and A x BS y Wherein the byproduct ACl can be dissolved in an organic solvent to obtain a target product A x BS y 。
In some preferred embodiments, the NaNi a Fe b Mn c O 2 The preparation of (2) comprises: will prepare the NaNi a Fe b Mn c O 2 Mixing the metal salts according to a proportion, heating to 800-1200 ℃ at a heating rate of 0.01-10 ℃/min, and preserving heat for 0.5-48 h to obtain the NaNi a Fe b Mn c O 2 。
In some preferred embodiments, the metal salt is mixed uniformly by ball milling stirring at a rotational speed of 100 to 1000rpm for a period of 0.2 to 3 hours.
In some preferred embodiments, the metal salt comprises sodium salt and NaNi a Fe b Mn c O 2 Metal salts of other metal elements; the sodium salt is one or more of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate, the metal salt of other metal elements is one or more of nickel-containing salt, iron-containing salt and manganese-containing salt, the nickel-containing salt can be one or more of nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel hydroxide, nickel carbonyl and nickel oxide, the iron-containing salt can be one or more of iron oxide, ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate, and the manganese-containing salt can be one or more of potassium permanganate, potassium manganate and manganese oxide.
The metal salt more preferably comprises sodium salt and precursor metal salt, wherein the metal element in the precursor metal salt is NaNi a Fe b Mn c O 2 The metal elements other than sodium are selected from nickel oxide, nickel iron manganese oxide, iron oxide, manganese iron oxide, nickel manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron manganese hydroxide and nickel manganese hydroxide; for example, when the O3 phase layered oxide cathode material is NaNi 0.34 Fe 0.33 Mn 0.33 O 2 When the precursor metal salt is preferably nickel hydroxide iron manganese or nickel iron manganese oxide.
In some preferred embodiments, the metal salt is according to the NaNi a Fe b Mn c O 2 The molar ratio of each metal element is weighed, wherein the sodium salt content is slightly larger than the requiredMolar mass to compensate for sodium loss during sintering. For example, when the positive electrode material is NaNi 0.34 Fe 0.33 Mn 0.33 O 2 When the metal salt is selected from sodium hydroxide, nickel oxide, ferrous oxide and manganese oxide, the molar ratio of the sodium hydroxide, the nickel oxide, the ferrous oxide and the manganese oxide is preferably 1-1.1:0.34:0.33:0.33.
In addition, the embodiment of the invention also provides a positive electrode plate, which comprises the modified O3 type sodium ion battery layered oxide positive electrode material and/or the modified O3 type sodium ion battery layered oxide positive electrode material prepared by the preparation method.
Specifically, the positive electrode plate comprises a positive electrode current collector and a positive electrode active material layer arranged on at least one side of the current collector; the positive electrode active material layer is coated on the current collector through positive electrode slurry, and is obtained after drying and cold pressing; the positive electrode slurry comprises a modified O3 type sodium ion battery layered positive electrode material, a conductive agent, a binder and a solvent.
Wherein the positive current collector can be selected to be aluminum foil; the conductive agent may be selected from conductive carbon such as carbon black, carbon nanotubes, graphene, etc.; the binder may be selected to be polyvinylidene chloride (PVDF); the solvent may be selected to be N-methylpyrrolidone (NMP).
In some preferred embodiments, the modified O3 type sodium ion battery layered positive electrode material, conductive carbon and PVDF are dissolved in a certain amount of NMP according to a mass ratio of 90:5:5, and the mixture is uniformly stirred to obtain positive electrode slurry, and then the positive electrode slurry is coated on a positive electrode current collector, dried and cut into pieces to obtain a positive electrode sheet.
The embodiment of the invention also provides a sodium ion battery, which comprises the positive pole piece.
Specifically, the sodium ion battery comprises a shell, a positive electrode plate, a diaphragm, a negative electrode plate and electrolyte. And stacking the positive electrode plate, the diaphragm and the negative electrode plate, forming a bare cell by lamination or winding, loading the bare cell into a shell, and injecting electrolyte to obtain the battery.
The negative electrode plate comprises a current collector and a negative electrode active material layer, wherein the current collector can be copper foil, the negative electrode active material layer is coated on the current collector through negative electrode active slurry, and the current collector is obtained through drying and cold pressing. The negative electrode active slurry comprises a negative electrode material, a conductive agent, a binder, a dispersing agent and a solvent; the negative electrode material may be soft carbon, hard carbon, composite carbon, or the like, the conductive agent may be conductive carbon, such as conductive carbon black, conductive graphite, vapor grown carbon fiber, carbon nanotube, or the like, the binder may be styrene-butadiene rubber (SBR), the dispersant may be sodium carboxymethyl cellulose (CMC), and the solvent may be water.
In some preferred embodiments, the anode hard carbon material, the conductive carbon and CMC/SBR are dissolved in a certain amount of water according to a mass ratio of 85:10:5, the anode slurry is obtained after uniform stirring, and then the anode slurry is coated on an anode current collector, dried and cut into pieces to obtain an anode pole piece.
In some preferred embodiments, the electrolyte is obtained by dissolving 1M sodium hexafluorophosphate in a solvent having a volume ratio of Ethylene Carbonate (EC) to diethyl carbonate (DEC) =1:1+5% fluoroethylene carbonate (FEC).
In some preferred embodiments, a winding process is adopted to prepare a bare cell, the diaphragm is firstly wound for 5/6 times, then the positive pole piece and the negative pole piece are sequentially wound for 8 times, and finally the positive pole piece is wound, so that the negative pole piece is completely wrapped in the positive pole piece. The prepared winding core is welded with the tab and glued, then is sealed by an aluminum plastic film, is taken out after being baked for 40 to 120 hours in a vacuum oven, and is tested for water content (requirement H 2 O<200 ppm), then injecting liquid according to a certain liquid injection coefficient and proportion, sealing, aging, forming and capacity-dividing testing to obtain the sodium ion battery.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
The present embodiment relates to Li 2 SiS 3 Coating modified O3 type sodium ion battery layered oxide positive electrode material (Li) 2 SiS 3 Preparation of @ NNFM-1), the specific procedure is as follows:
(1) Nickel hydroxideAdding ferromanganese and sodium carbonate into a reaction vessel according to a molar ratio of 1:0.535, ball-milling and stirring at 600rpm for 2.4h, heating to 980 ℃ at 4.5 ℃/min after uniform mixing, and carrying out solid-state sintering treatment at 10.5h to obtain NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Powder (NNFM-1).
(2) In a glove box (water oxygen value is less than or equal to 0.01 ppm), 5mg of polished and refined metal lithium powder is immersed into Li 2 S 8 In tetrahydrofuran solution, centrifugally stirred for 10 hours to passivate the surface of Li and form a uniform polysulfide layer (Li 2 S x ) A mixed solution was obtained. Subsequently, siCl is added 4 Tetrahydrofuran solution was added to the mixed solution and centrifuged and shaken for about 25 minutes to effect the reaction, forming thermodynamically stable LiCl and product Li 2 SiS 3 LiCl was dissolved in solvent tetrahydrofuran and removed.
(3) Li is mixed with 2 SiS 3 Mixing with NNFM-1 powder material, grinding for 12min, transferring into sintering furnace, and heating to 650deg.C at 30deg.C/min to obtain Li 2 SiS 3 @NNFM-1。
NNFM-1 and Li prepared in this example 2 SiS 3 Li (lithium ion battery) 2 SiS 3 Test characterization is carried out on @ NNFM-1, and the characterization result is as follows:
FIGS. 1 and 2 are respectively a flow chart and a graph of test results of an ICP test of NNFM-1 prepared in this example, and as can be seen from FIG. 2, the powder sample prepared in step (1) of this example is NaNi 0.34 Fe 0.33 Mn 0.33 O 2 。
FIG. 3 is the product Li prepared in step (2) of this example 2 SiS 3 As can be seen from fig. 3a, the surface of the material has a porous structure, and the crystal plane parameters corresponding to the lattice fringes in fig. 3b are equal to Li 2 SiS 3 The crystal structure of the materials is consistent; FIG. 4 is a Mapping graph of the material, and it can be seen that three elements Si/S/Li are uniformly distributed in the material. As can be seen from the characterization results of FIGS. 3 and 4, the present example successfully prepared Li 2 SiS 3 A material.
FIG. 5 shows Li obtained in the step (3) of this example 2 SiS 3 X-ray diffraction pattern of @ NNFM-1 material, it can be seen from the figure that most of diffraction peaks of the material can correspond to the standard card of O3 phase, but partial diffraction peaks are offset due to small amount of Li 2 SiS 3 Introduction results in; in addition, the partial appearance identified by the dashed box in the figure can be attributed to Li 2 SiS 3 This also indicates that the material has NNFM-1 as the main body, but Li is present on the surface 2 SiS 3 Coating phenomenon. FIG. 6 is an X-ray photoelectron spectrum of the material, showing that the main chemical composition of the coating layer is Li 2 SiS 3 Li in a small amount 4 SiS 4 、SiS 2 And Li (lithium) 2 S。
Example 2
The present embodiment relates to Li 2 SiS 3 Coating modified O3 type sodium ion battery layered oxide positive electrode material (Li) 2 SiS 3 Preparation of @ NNFM-2) differs from example 1 only in step (1) NaNi 0.34 Fe 0.33 Mn 0.33 O 2 The preparation process of (2) comprises the following specific operations:
(1) Adding sodium carbonate, nickel nitrate, ferrous oxalate and manganese oxide into a reaction vessel according to the molar ratio of 0.535:0.34:0.33:0.33, ball milling and stirring at 600rpm for 2.4 hours, heating to 980 ℃ at 4.5 ℃/min after uniform mixing, and carrying out solid-state sintering treatment at the temperature of 10.5 hours to obtain NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Powder (NNFM-2).
Steps (2) and (3) were identical to example 1.
Example 3
Compared with example 1, mnPS is used 3 Replacement of Li 2 SiS 3 The rest steps are the same, and a modified anode material MnPS is prepared 3 @NNFM-1。
Example 4
Compared with example 1, niPS is used 3 Replacement of Li 2 SiS 3 The rest steps are the same, and a modified cathode material NiPS is prepared 3 @NNFM-1。
Example 5
In comparison with example 1, cu was used 3 SbS 3 Replacement of Li 2 SiS 3 The other steps are the same, and the modified anode material Cu is prepared 3 SbS 3 @NNFM-1。
Example 6
In comparison with example 1, in was used 2 PS 3 Replacement of Li 2 SiS 3 The rest steps are the same, and a modified anode material In is prepared 2 PS 3 @NNFM-1。
Example 7
Compared with example 1, bi is used 4 TeS 13 Replacement of Li 2 SiS 3 The rest steps are the same, and the modified anode material Bi is prepared 4 TeS 13 @NNFM-1。
Example 8
Compared with example 1, pb was used 2 SnS 2 Replacement of Li 2 SiS 3 The rest steps are the same, and a modified anode material Pb is prepared 2 SnS 2 @NNFM-1。
Example 9
Compared with example 1, gaPS is used 4 Replacement of Li 2 SiS 3 The rest steps are the same, and the modified anode material GaPS is prepared 4 @NNFM-1。
Example 10
In comparison with example 1, fe is used 3 SiS 2 Replacement of Li 2 SiS 3 The rest steps are the same, and a modified anode material Fe is prepared 3 SiS 2 @NNFM-1。
Comparative example 1
This comparative example was prepared by the preparation method of example 1 to obtain O3 phase layered oxide NaNi 0.34 Fe 0.33 Mn 0.33 O 2 (NNFM-1)。
Application and performance characterization
1. Assembly of soft package battery core
Preparation of a positive plate: the materials prepared in the examples and the comparative examples are respectively used as positive electrode active substances to prepare positive electrode plates, the positive electrode active substances, conductive carbon and PVDF are dissolved in N-methyl pyrrolidone according to the mass ratio of 90:5:5, and the positive electrode plates are obtained by coating, drying and cutting the materials after uniform stirring.
Preparing a negative plate: and dissolving the anode hard carbon material, the conductive carbon and the CMC/SBR binder in water according to a ratio of 85:10:5, uniformly stirring, and then coating, drying and cutting to obtain the anode sheet.
Preparation of electrolyte: 1M sodium hexafluorophosphate is adopted to dissolve in a solution of ethylene carbonate and propylene carbonate plus 5 percent fluoroethylene carbonate in a volume ratio of 1:1, so as to obtain electrolyte.
The pole piece adopts a winding process, the diaphragm is firstly wound for 5/6 circles, then the anode and the cathode are sequentially wound for 8 circles, and finally the anode is wound, so that the cathode piece is completely wrapped in the anode. The prepared winding core is welded with the tab and glued, then is sealed by an aluminum plastic film, is taken out after being baked in a vacuum oven for 40 to 120 hours, and is tested for water content (requirement H 2 O<200 ppm), and then injecting liquid according to a certain liquid injection coefficient and proportion, sealing, aging, forming and capacity-dividing testing.
2. Performance testing
The assembled battery is placed on a blue standard tester for 8 hours, and then starts to test, and is charged and discharged at a rate of 0.1C, wherein the theoretical specific capacity is 130/370mAh/g (the capacity is designed according to the pre-calculation). And charging and discharging at first by adopting a current of 0.1C, and finally, reading and calculating a corresponding capacity value.
The initial specific capacity of each cell in the voltage interval of 2 to 4V, the first coulombic efficiency and the specific discharge capacity at cycle 100/300/500/1000 are tested, and the test results are summarized in table 1 below:
table 1 shows the performance of sodium ion batteries prepared from the positive electrode materials of examples 1 to 10 and comparative example 1
Figure BDA0004095136640000141
As is clear from the above table, examples 1 to 10 utilize A compared to the unmodified NNFM-1 material in comparative example 1 x BS y The NNFM-1 or NNFM-2 material is coated and modified by the material through a solid-phase sintering method, so that the discharge specific capacity, initial coulomb efficiency and cycle stability of the sodium ion battery are effectively improved. Wherein Li prepared in example 1 2 SiS 3 The sodium ion battery prepared by taking the @ NNFM-1 as the positive electrode active substance shows optimal electrochemical performance, achieves an initial specific capacity of 140.5mA h/g, improves 20.8% compared with comparative example 1, improves the initial coulombic efficiency from 71.4% to 86.1%, and has a capacity retention rate after 1000 cycles still as high as 85.9%.
In conclusion, the invention can stably exist A by coating air on the surface of the O3 type sodium ion battery layered oxide positive electrode material x BS y The prepared modified anode material has excellent electrochemical performance in a full battery with hard carbon as a cathode material, so that the discharge specific capacity and initial coulomb efficiency of the sodium ion battery are improved, and the cycling stability of the sodium ion battery is effectively improved.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.

Claims (12)

1. A modified O3 type sodium ion battery layered oxide positive electrode material is characterized in that the positive electrode material comprises A x BS y @NaNi a Fe b Mn c O 2 Wherein A is selected from one or more of alkali metal element, transition metal element and In, bi, pb, ga, B is selected from one or more of P, si, C, N, sb, se, ge, te, sn, x and y are larger than or equal to 1,0 is smaller than or equal to a, B and c is smaller than or equal to 1, and a+b+c=1.
2. The modified O3 type sodium ion battery layered oxide cathode material according to claim 1, wherein the alkali metal element is Li, na; the transition metal element is Mn, ni, cu, fe.
3. The modified O3 sodium ion battery layered oxide cathode material of claim 1, wherein a is x BS y Comprises Li 2 SiS 3 、Li 4 SiS 4 、MnPS 3 、NiPS 3 、Cu 3 SbS 3 、In 2 PS 3 、Bi 4 TeS 13 、Pb 2 SnS 2 、GaPS 4 、Fe 3 SiS 2 At least one of them.
4. The modified O3 sodium ion battery layered oxide cathode material of claim 1, wherein a is x BS y Comprises Li 2 SiS 3 And a=0.34, b=c=0.33.
5. The modified O3 sodium ion battery layered oxide cathode material of claim 1, wherein a is x BS y @NaNi a Fe b Mn c O 2 The particle diameter D50 of the particles is 0.01-58.27 mu m, and the specific surface area is 0.01-33.68 m 2 Per gram, the water content is 0.01 to 1.58 percent.
6. A method for preparing a modified O3 type sodium ion battery layered oxide positive electrode material according to any one of claims 1 to 5, which is characterized in that A is prepared by x BS y With NaNi a Fe b Mn c O 2 Uniformly mixing, and obtaining the A through solid phase sintering x BS y @NaNi a Fe b Mn c O 2 。
7. The method of claim 6, wherein a is x BS y With NaNi a Fe b Mn c O 2 The feeding molar ratio of (2) is 0.01-0.1:1; the solid phase sintering step comprises the following steps: the temperature rising rate is 10-30 ℃/min, and the sintering temperature is 300-800 ℃.
8. The method of claim 6, wherein a is x BS y The preparation of (2) comprises:
impregnating metal A powder with A-containing x S y Obtaining a mixed solution in the organic solvent of (2);
will contain BCl z Adding the organic solvent into the mixed solution, and obtaining A through reaction x BS y ；
The BCl z A chloride of B; the organic solvent is selected from one or more of methanol, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, isopropyl acetate, dimethylformamide, propylene glycol, pyridine and diethyl ether.
9. The method according to claim 6, wherein the NaNi a Fe b Mn c O 2 The preparation of (2) comprises: will prepare the NaNi a Fe b Mn c O 2 Mixing the metal salts according to a proportion, heating to 800-1200 ℃ at a heating rate of 0.01-10 ℃/min, and preserving heat for 0.5-48 h to obtain the NaNi a Fe b Mn c O 2 。
10. The method according to claim 9, wherein the metal salt comprises sodium salt and precursor metal salt, and the metal element in the precursor metal salt is NaNi a Fe b Mn c O 2 Other metal elements except sodium; the sodium salt is one or more of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate, and the precursor metal salt is one or more of nickel oxide, nickel iron manganese oxide, ferric oxide, manganese iron oxide, nickel manganese oxide, nickel hydroxide, ferric hydroxide, manganese hydroxide, nickel iron manganese hydroxide and nickel manganese hydroxide.
11. The positive electrode plate is characterized by comprising the modified O3 type sodium ion battery layered oxide positive electrode material prepared by the preparation method of any one of claims 1 to 5 and/or the modified O3 type sodium ion battery layered oxide positive electrode material prepared by the preparation method of any one of claims 6 to 10.
12. A sodium ion battery comprising the positive electrode sheet of claim 11.
CN202310163721.3A 2023-02-24 2023-02-24 Modified O3 type sodium ion battery layered oxide positive electrode material and preparation method and application thereof Pending CN116230892A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117285087A (en) * 2023-11-24 2023-12-26 北京中科海钠科技有限责任公司 Layered oxide, preparation method thereof and sodium battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117285087A (en) * 2023-11-24 2023-12-26 北京中科海钠科技有限责任公司 Layered oxide, preparation method thereof and sodium battery
CN117285087B (en) * 2023-11-24 2024-04-23 北京中科海钠科技有限责任公司 Layered oxide, preparation method thereof and sodium battery

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