CN115954463B - Sodium ion battery layered oxide composite material, preparation method thereof, positive plate and sodium ion battery - Google Patents
Sodium ion battery layered oxide composite material, preparation method thereof, positive plate and sodium ion battery Download PDFInfo
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Abstract
The invention discloses a layered oxide composite material of a sodium ion battery, the molecular formula of which is M x B y /NaNi a Fe b Mn c O 2 Wherein: m is an alkali metal element, x is more than or equal to 1 and y is more than or equal to 9; 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1. The invention also discloses a preparation method of the sodium ion battery layered oxide composite material, and a positive plate and a sodium ion battery prepared from the sodium ion battery layered oxide composite material. The layered oxide composite material of the sodium ion battery can improve the high-temperature stability of the layered oxide and improve the high-temperature cycle performance and capacity of the sodium ion battery.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a layered oxide composite material of a sodium ion battery, a preparation method of the layered oxide composite material, a positive plate and a sodium ion battery.
Background
Among various positive electrode materials of sodium ion batteries, O3-phase layered oxides have received attention because they can provide sufficient sodium in a full battery, have high electrochemical activity, have high theoretical specific capacities, and are easy to synthesize. However, the problems of low energy density and poor high temperature stability limit the practical application of the O3 phase layered oxide.
Therefore, how to improve the high-temperature cycle performance and the energy density of the O3 phase layered oxide cathode material becomes one of the key problems in the related art of sodium ion batteries.
Disclosure of Invention
The invention aims to provide a layered oxide composite material of a sodium ion battery, so as to improve the high-temperature stability of layered oxide and improve the high-temperature cycle performance and capacity of the sodium ion battery.
In order to solve the technical problems, the invention provides the following technical scheme:
the first aspect of the invention provides a layered oxide composite material of a sodium ion battery, wherein the molecular formula of the layered oxide composite material of the sodium ion battery is M x B y /NaNi a Fe b Mn c O 2 Wherein: m is an alkali metal element, x is more than or equal to 1 and y is more than or equal to 9; 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
Further, the D50 particle size of the layered oxide composite material of the sodium ion battery is 0.01-25.5 mu m;
and/or the specific surface area of the sodium ion battery layered oxide composite material is 0.01-47.4 m 2 /g；
And/or, the water content of the sodium ion battery layered oxide composite material is 0.01% -1.25%.
The second aspect of the invention provides a preparation method of a layered oxide composite material of a sodium ion battery, which comprises the following steps:
s1, mixing alkali metal M powder and boron powder in vacuum or inert atmosphere, and performing vacuum hot extrusion to obtain M x B y A compound;
s2. M x B y Compounds, naNi a Fe b Mn c O 2 After mixing the powder, carrying out hot extrusion to obtain the layered oxide composite material of the sodium ion battery;
in the step S1, x is more than or equal to 1 and y is more than or equal to 9;
in step S2, 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
Further, in the step S1, the molar ratio of the alkali metal M powder to the boron powder is 1-10:1-6;
and/or the temperature of the vacuum hot extrusion is 1000-1500 ℃, the pressure is 10-500 Mpa, and the heat preservation time is 0.5-6 h.
Further, in the step S2, the temperature of the hot extrusion is 700-1200 ℃, the pressure is 10-500 Mpa, and the heat preservation time is 0.5-48 h;
and/or the heating rate of the hot extrusion is 0.01-10 ℃/min.
Further, in step S2, the NaNi a Fe b Mn c O 2 One method of preparing the powder is:
a. mixing sodium salt and metal salt, and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein in the step a, the sodium salt comprises at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulphite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide and sodium iodide;
and/or the nickel salt comprises at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide and nickel carbonyl;
and/or the ferric salt comprises at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate;
and/or the manganese salt comprises at least one of manganese oxide, potassium permanganate and potassium manganate;
and/or the molar ratio of the sodium salt to the metal salt is 0.05-1.25:0.01-1.
Further, the NaNi a Fe b Mn c O 2 Another preparation method of the powder comprises the following steps:
c. mixing sodium salt with precursor salt, and stirring uniformly;
d. c, sintering the mixture obtained in the step c to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein the sodium salt comprises at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate;
and/or the precursor salt comprises at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese iron hydroxide, nickel manganese hydroxide and nickel iron manganese hydroxide;
and/or the molar ratio of the sodium salt to the precursor salt is 0.01-1.25:0.01-1.
Further, in the steps b and d, the sintering temperature is 800-1200 ℃ and the sintering time is 0.5-48 h;
and/or the temperature rising rate of the sintering is 0.01-10 ℃/min.
The third aspect of the invention provides a positive plate, which comprises the sodium ion battery layered oxide composite material or the sodium ion battery layered oxide composite material prepared by the method.
According to a fourth aspect of the invention, there is provided a sodium ion battery comprising the positive electrode sheet described above.
Compared with the prior art, the invention has the beneficial effects that:
1. in the sodium ion battery layered oxide composite material, the B-alkali metal compound with the 3D framework structure is introduced, so that the composite material has good mechanical and thermal stability, and the phase and structure of the composite material can endure the high temperature of more than 400 ℃ and keep unchanged, so that the high-temperature stability of the O3 phase layered oxide can be greatly optimized, and the high-temperature cycle performance of the battery is improved.
2. In the sodium ion battery layered oxide composite material, the existence of alkali metal generates a pre-alkali metal effect, so that the energy density of the material can be improved, and the capacity and the first coulombic efficiency of the battery are improved.
Drawings
FIG. 1 shows a vacuumPreparation of M by Hot extrusion apparatus x B y A schematic of the material;
FIG. 2 is a diagram of example 1 material Na 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Is characterized in that: FIG. 2 a is a flow chart of the preparation of the material; b and c in fig. 2 are Scanning Electron Microscope (SEM) images of the material; fig. 2 d is a Transmission Electron Microscope (TEM) of the material;
FIG. 3 shows a material Na according to example 1 of the present invention 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2 X-ray diffraction pattern (XRD) of (a).
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 in the description of the invention herein 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 O3 phase layered oxide has the problems of low energy density, poor high-temperature stability and the like, and limits the practical application thereof. At present, the prior art adopts means such as element doping and coating to modify the O3 phase layered oxide, but the means can only slightly improve the energy density, but can not solve the problem of poor high-temperature stability, and particularly the material system formed by the material system and the hard carbon material in practical application.
In order to solve the above problems of the layered oxide, the present invention provides a modification method of the layered oxide, which improves the high temperature stability of the layered oxide by introducing an alkali metal-B compound having a 3D framework structure, thereby improving the high temperature cycle performance of the battery.
Specifically, the molecular formula of the layered oxide composite material of the sodium ion battery provided by the invention is M x B y /NaNi a Fe b Mn c O 2 Wherein: m is an alkali metal element, x is more than or equal to 1 and y is more than or equal to 9; 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
In the invention, naNi a Fe b Mn c O 2 Is a layered oxide comprising an O3 phase layered oxide, a P2 phase layered oxide, e.g. NaMnO 2 、NaFeO 2 、NaNiO 2 、NaFe 1/2 Mn 1/2 O 2 Etc.
M x B y The compound with the 3D porous framework structure is produced by the reaction of alkali metal powder and boron powder, has good mechanical stability and thermal stability, and can bear the high temperature of more than 400 ℃ and maintain unchanged phase and structure. Thus, the present invention employs M x B y Modifying the layered oxide with M x B y The high-temperature battery cell has the advantages that the high-temperature battery cell has excellent thermal stability and higher electrochemical decomposition potential, so that the stability of the structure can be maintained when the electrode works at high temperature, and the high-temperature cycle performance of the battery cell is improved; second, M x B y The conductive material also has high conductivity, and can improve the conductivity of the layered oxide; in addition, M x B y The synergistic effect of the alkali metal M and the 3D framework can lead the layered oxide anode material to generate a pre-alkali metal effect, thereby improving the energy density and the first coulombic efficiency of the battery.
In the present invention, the D50 particle size of the layered oxide composite material for sodium ion battery may be in the range of 0.01 to 25.5. Mu.m, for example, 0.01 to 0.1. Mu.m, 0.1 to 1. Mu.m, 1 to 5. Mu.m, 5 to 10. Mu.m, 10 to 20. Mu.m, 25.5. Mu.m, etc.
In the invention, the specific surface area of the layered oxide composite material of the sodium ion battery can be in the range of 0.01 to 47.4 and 47.4 m 2 For example, the ratio of the total amount of the components per gram is 0.01 to 0.1. 0.1 m 2 /g、0.1～1 m 2 /g、1～5 m 2 /g、5～10 m 2 /g、10～20 m 2 /g、20～40 m 2 /g、40～47.4 m 2 /g, etc.
In the present invention, the water content of the layered oxide composite material for sodium ion battery may be 0.01% to 1.25%, for example, 0.01%, 0.05%, 0.1%, 0.2%, 0.4%, 0.5%, 0.8%, 1.0%, 1.25%, etc.
The invention also discloses a preparation method of the sodium ion battery layered oxide composite material, which comprises the following steps:
s1, mixing alkali metal M powder and boron powder in vacuum or inert atmosphere, and performing vacuum hot extrusion to obtain M x B y A compound;
s2. M x B y Compounds, naNi a Fe b Mn c O 2 And mixing the powder, and performing hot extrusion to obtain the layered oxide composite material of the sodium ion battery.
In the above step S1, since alkali metal is easily oxidized in air, the step needs to be performed in vacuum or an inert atmosphere (He, ne, ar, etc.) to avoid oxidation of alkali metal. In a preferred embodiment, this step may be performed in a glove box. The molar ratio of the alkali metal M powder (m=li, na, K) to the boron powder may be 1 to 10:1 to 6, and may be, for example, 10:1, 8:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, 1:6, or the like. In order to promote a sufficient contact reaction of the alkali metal powder with the boron powder, it is preferable that the alkali metal powder and the boron powder are selected as nano-sized powders.
After the alkali metal M powder and the boron powder are fully and uniformly mixed, the mixture is preferably placed in a vacuum hot extrusion device for vacuum hot extrusion treatment. As shown in FIG. 1, in the vacuum hot extrusion apparatus, an alkali metal M powder and a boron powder are extruded to be in sufficient contact with each other, and a solid phase sintering reaction occurs under heating to form M x B y A compound. Wherein the pressure applied by the equipment to the powder during sintering can be 10-500 Mpa, such as 10 Mpa, 20 Mpa, 50Mpa, 100 Mpa, 200 Mpa, 300 Mpa, 400 Mpa, 500Mpa, etc. The sintering temperature may be 1000 to 1500 ℃, for example 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, etc. The heating rate may be 0.01 to 10℃per minute, for example, 0.01℃per minute, 0.1℃per minute, 0.5℃per minute, 1℃per minute, 2℃per minute, 5℃per minute, 10℃per minute, etc. The incubation time may be 0.5 to 6h, for example 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, etc. M obtained in this step x B y The compound is a substance which is easy to crush, and is crushed, ground and sieved to obtain powdery substances.
In the step S2 of the invention, M is x B y Powder, naNi a Fe b Mn c O 2 And (5) after the powder is stirred and mixed, placing the mixture in a hot extrusion furnace for heat treatment. In a hot extrusion furnace, the holding time may be 0.5 to 48h, for example 0.5h, 1h, 2h, 4h, 6h, 8h, 10h, 12h, 18h, 24h, 30h, 40h, 48h, etc.
In this step, M x B y Powder, naNi a Fe b Mn c O 2 Mixing the powder, hot-pressing and sintering, and then partially preparing NaNi a Fe b Mn c O 2 Powder into M x B y In the pores of the framework structure (as in b-d of fig. 2).
In the invention, naNi a Fe b Mn c O 2 The powder may be prepared by two methods, one based on metal salt mixing and the other based on precursor salt mixing.
The method based on metal salt mixing comprises the following steps:
a. mixing sodium salt with metal salt, ball milling and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a to obtain the NaNi a Fe b Mn c O 2 And (3) powder.
In the step a, the sodium salt includes at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulphite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide and sodium iodide. Nickel salts include, but are not limited to, at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide, nickel carbonyl; iron salts include, but are not limited to, at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate, and ferrous oxalate; manganese salts include, but are not limited to, at least one of manganese oxide, potassium permanganate, potassium manganate.
In the step a, the sodium salt and the metal salt are prepared according to NaNi a Fe b Mn c O 2 The stoichiometric ratio in (0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1) is dosed. In some embodiments, the molar ratio of sodium salt to metal salt is from 0.05 to 1.25:0.01 to 1. For example, in the preparation of the compound NaFeO 2 When sodium sulfate is used as sodium salt and ferric chloride is used as metal salt, the mixing mole ratio of the sodium salt to the metal salt is 1:2.
In the step b, the temperature rising rate of the sintering is preferably 0.01 to 10 ℃ per minute, and for example, may be 0.01 ℃ per minute, 0.1 ℃ per minute, 0.5 ℃ per minute, 1 ℃ per minute, 2 ℃ per minute, 5 ℃ per minute, 10 ℃ per minute, etc.; the sintering temperature is preferably 800 to 1200 ℃, and may be 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or the like; the sintering time is preferably 0.5 to 48 and h, and may be, for example, 0.5h, 1h, 2h, 5h, 10h, 20h, 30h, 40h, 48h, etc.
The method based on precursor salt mixing comprises the following steps:
c. mixing sodium salt with precursor salt, ball milling and stirring uniformly;
d. c, sintering the mixture obtained in the step c to obtain NaNi a Fe b Mn c O 2 And (3) powder.
In the step c, the sodium salt includes at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate. The precursor salt includes, but is not limited to, at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese nickel hydroxide, and nickel iron manganese hydroxide.
In the step c, the sodium salt and the precursor salt are prepared according to NaNi a Fe b Mn c O 2 The stoichiometric ratio in (0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1) is dosed. In some embodiments, the molar ratio of sodium salt to precursor salt is 0.01 to 1.25:0.01 to 1. For example, in the preparation of the compound NaFe 1/2 Mn 1/2 O 2 When the sodium sulfate is used as sodium salt and the ferromanganese oxide is used as precursor salt, the mixing mole ratio of the sodium salt to the precursor salt is 1:1.
In the step d, the temperature rising rate of the sintering is preferably 0.01 to 10 ℃ per minute, and for example, may be 0.01 ℃ per minute, 0.1 ℃ per minute, 0.5 ℃ per minute, 1 ℃ per minute, 2 ℃ per minute, 5 ℃ per minute, 10 ℃ per minute, etc.; the sintering temperature is preferably 800 to 1200 ℃, and may be 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or the like; the sintering time is preferably 0.5 to 48 and h, and may be, for example, 0.5h, 1h, 2h, 5h, 10h, 20h, 30h, 40h, 48h, etc.
On the basis of the layered oxide composite material, the invention also provides a sodium ion battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the diaphragm is arranged to isolate the positive plate from the negative plate.
In the sodium ion battery, the positive plate can be prepared by adopting a common plate preparation process in the field. The preparation method is as follows: and mixing the layered oxide composite material, the conductive agent and the binder to prepare slurry, coating the slurry on at least one side surface of the positive electrode current collector, and drying and tabletting to obtain the positive electrode plate.
In the preparation method of the positive plate, the type and the content of the conductive agent are not particularly limited, and can be selected according to actual requirements. In some embodiments, the conductive agent includes at least one of conductive carbon black, carbon nanotubes, acetylene black, graphene, ketjen black, carbon nanofibers, and the like. It will be appreciated that other conductive agents capable of performing the functions of the present application may be selected as desired without limitation without departing from the spirit of the present application.
In the preparation method of the positive plate, the types and the content of the binder are not particularly limited, and can be selected according to actual requirements. In some embodiments, the binder includes at least one of polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, sodium carboxymethyl cellulose, polymethacrylate, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyamide, polyimide, polyacrylate, styrene butadiene rubber, sodium alginate, chitosan, polyethylene glycol, guar gum, and the like.
The type of the positive electrode current collector is not particularly limited, and may be selected according to practical requirements, for example, the positive electrode current collector may be an aluminum foil, a nickel foil or a polymer conductive film, and preferably the positive electrode current collector is an aluminum foil.
In the sodium ion battery, the type of separator is not particularly limited, and any separator material used in conventional batteries, such as polyethylene, polypropylene, polyvinylidene fluoride, nonwoven fabric, multilayer composite films thereof, and modified separators such as ceramic modification and PVDF modification of the separator may be used.
In the sodium ion battery, the electrolyte can be one or more of organic liquid electrolyte, organic solid electrolyte, solid ceramic electrolyte and gel electrolyte. Preferably, the electrolyte is an organic liquid electrolyte obtained by dissolving sodium salt in a nonaqueous organic solvent; wherein the sodium salt may comprise sodium difluorophosphate (NaPO) 2 F 2 ) Sodium hexafluorophosphate (NaPF) 6 ) One or more of sodium bis (fluorosulfonyl) imide (NaFSI), sodium bis (trifluoromethanesulfonyl) imide (naftsi), and sodium difluoro (NaDFOB) oxalato borate (NaDFOB). The nonaqueous organic solvent may include one or more of cyclic carbonate, chain carbonate, and carboxylate. Wherein the cyclic carbonate can be selected from one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), butylene carbonate and gamma-butyrolactone; the chain carbonate may be selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), methyl Propyl Carbonate (MPC), methyl Acetate (MA), ethyl Acetate (EA), and Ethyl Propionate (EP).
In some embodiments, a certain amount of additives may also be added to the organic liquid electrolyte. The additive may include one or more of Vinylene Carbonate (VC), vinyl carbonate (VEC), vinyl sulfate (DTD), ethylene Sulfite (ES), methylene Methane Disulfonate (MMDS), 1, 3-Propane Sultone (PS), propylene sultone (PES), propylene sulfate (TMS), trimethylsilyl phosphate (TMSP), trimethylsilyl borate (TMSB), fluoroethylene carbonate (FEC).
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.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used, unless otherwise specified, are commercially available.
1. XRD test method
Grinding the prepared powder material, transferring to a glass sheet object stage, and transferring to an X-ray diffractometer for scanning test, wherein the scanning range is 10-80 degrees, and the scanning speed is 5 degrees/min.
2. ICP test method
ICP detection is used to determine the molecular formula of the pre-alkali-metallized material, where ICP-AES is known collectively as inductively coupled plasma-atomic emission spectroscopy (Inductively Coupled Plasma-Atomic Emission Spectrometry), also known as inductively coupled plasma-emission spectroscopy (ICP-OES). The sample treatment process is as follows:
(1) Weighing: accurately weighing about 0.1g of sample in a 50ml polytetrafluoroethylene digestion tube, and recording the mass of the sample.
(2) To the weighed sample digestion tubes, an appropriate amount of mineral acid (typically 5ml of concentrated nitric acid/1 ml of hydrofluoric acid) was added, respectively. The lid was closed and placed in a stainless steel reaction kettle, and after heating in an oven at 190℃for about 10 hours, the heating and cooling was stopped.
(3) The cooled solution was transferred to a 25ml plastic volumetric flask and finally to volume with deionized water.
(4) Preparing a standard test solution, wherein the standard solution is a national standard substance, and the concentration points of the curve are respectively: 0. 0.5, 1.0, 2.0, 5.0mg/L;
(5) And (3) instrument testing, namely firstly preparing a standard solution calibration curve through an ICP-OES (inductively coupled plasma-optical emission spectrometry) instrument, inputting the mass and the volume of a sample, then sequentially testing the digested solution, and testing after dilution beyond the curve range.
(6) And determining the final content of the element to be tested in each sample through a spectrogram, and obtaining a test result.
3. Assembly and test of soft package battery core
The positive electrode material, the conductive carbon and the PVDF are weighed according to the mass ratio of 90:5:5, dissolved in a certain amount of NMP, stirred, coated, dried and cut into pieces. Then, the anode hard carbon material, the conductive carbon and CMC/SBR are weighed according to the mass ratio of 85:10:5, dissolved in a certain amount of water, stirred, coated, dried and cut into pieces. The pole piece adopts a winding process, the diaphragm is firstly wound for 5/6 circles, then the positive pole and the negative pole are sequentially wound for 8 circles, and finally the positive pole is wound, so that the negative pole piece is completely wrapped in the positive pole. 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), and then injecting liquid according to a certain liquid injection coefficient and proportion, sealing, aging, forming and capacity-dividing testing. Wherein the electrolyte is 1M sodium hexafluorophosphate dissolved in the volume ratio EC: dec=1:1+5% fec in solvent.
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 130/370 mAh/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.
Example 1: preparation of Na based on precursor salts 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2
(1) And adding precursor salt of nickel hydroxide iron manganese and sodium carbonate into a reaction container according to the molar ratio of 1:0.55, and stirring and mixing uniformly. Then, the mixture is subjected to solid state sintering treatment, the heating temperature is 1000 ℃, the heating rate is 5.5 ℃/min, and the heat preservation time is 12.5 hours, thus obtaining NaNi 0.34 Fe 0.33 Mn 0.33 O 2 A powder;
(2) Mixing nano sodium powder and B powder according to a molar ratio of 5:4 in a glove box; transferring the mixture into a vacuum extrusion device, and sintering at 1500deg.C under 250Mpa for 3.5 hr to obtain 3D frameNa of frame structure 5 B 4 A compound;
(3) Na is mixed with 5 B 4 Compound and NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Uniformly stirring and mixing the powder, transferring the powder into a vacuum hot extrusion sintering furnace, heating to 900 ℃ at a heating rate of 10 ℃/min, and carrying out heat preservation and sintering for 4 hours under the condition of 180Mpa to obtain Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 And (3) powder.
Example 2: preparation of Na based on Metal salts 5 B 4 / NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 2 differs from example 1 in that: in the step (1), sodium carbonate, nickel nitrate, ferrous oxalate and manganese oxide with the molar ratio of 0.55:0.34:0.33:0.33 are used as raw materials to prepare NaNi 0.34 Fe 0.33 Mn 0.33 O 2 The other steps are the same.
Example 3: preparation of K 5 B 4 //NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 3 differs from example 1 in that: the step (2) adopts nano potassium powder.
Example 4: preparation of K 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 4 differs from example 2 in that: the step (2) adopts nano potassium powder.
Example 5: preparation of Li 5 B 4 //NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 5 differs from example 1 in that: the step (2) adopts nano lithium powder.
Example 6: preparation of K 3 B 2 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 6 differs from example 1 in that: the nano potassium powder is adopted in the step (2), and the molar ratio of the nano potassium powder to the B powder is 3:2.
Example 7: preparation of Na 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 7 differs from example 1 in that: in the step (2), the molar ratio of the nano sodium powder to the B powder is 2:1.
Example 8: preparation of Na 3 B 2 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 8 differs from example 1 in that: in the step (2), the molar ratio of the nano sodium powder to the B powder is 3:2.
Example 9: preparation of K 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 9 differs from example 1 in that: the nano potassium powder is adopted in the step (2), and the molar ratio of the nano potassium powder to the B powder is 2:1.
Example 10: preparation of Li 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2
Example 10 differs from example 1 in that: the step (2) adopts nano lithium powder, and the molar ratio of the nano lithium powder to the B powder is 2:1.
Comparative example 1: preparation of NaNi 0.34 Fe 0.33 Mn 0.33 O 2
The preparation method is the same as in the step (1) of the example 1.
The following is directed to NaNi prepared in example 1 0.34 Fe 0.33 Mn 0.33 O 2 Na and Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Characterization testing was performed.
Table 1 shows NaNi 0.34 Fe 0.33 Mn 0.33 O 2 ICP test results of the material. As can be seen from the results in the table, the layered oxide material prepared in step (1) of example 1 has a molecular formula of NaNi 0.34 Fe 0.33 Mn 0.33 O 2 。
TABLE 1
In FIG. 2 a is Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 And (3) preparing a composite material.
In FIG. 2 b and c are Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Scanning Electron Microscope (SEM) of the composite material, from which it can be seen that NaNi 0.34 Fe 0.33 Mn 0.33 O 2 The material is uniformly adhered to Na 5 B 4 Is in the 3D framework of (c).
In FIG. 2 d is Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Transmission Electron Microscopy (TEM) of the composite material, from which it can be seen that NaNi 0.34 Fe 0.33 Mn 0.33 O 2 And Na (Na) 5 B 4 Is bonded together.
FIG. 3 is Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 The XRD diffraction pattern of the composite material is basically consistent with the standard peak of the O3 phase standard card, and is consistent with the existing literature; in addition, naNi 0.34 Fe 0.33 Mn 0.33 O 2 Is shifted due to Na incorporation 5 B 4 So that the characteristic peaks are shifted.
Na prepared in example 1 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 As a positive electrode active material, the assembled sodium ion pouch cell achieved an initial specific capacity of about 140.5 mA h/g in the voltage interval of 2-4V. After the material is circulated for 100 circles at 25/45/60/100 ℃, the specific discharge capacity of the material is 133.6/129.2/120.4/107.98mA h/g respectively, and the material has very excellent high-temperature circulation performance.
Na prepared in example 2 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 As positive electrode active material, the assembled sodium ion soft package battery is solid in the voltage range of 2-4VAn initial specific capacity of approximately 126.2mA h/g was now obtained. After 100 cycles of circulation at 25/45/60/100 ℃, the specific discharge capacity of the material is 115.8/110.5/100.3/91.4 mA h/g respectively. And is somewhat lower than in example 1.
For comparison, naNi prepared in comparative example 1 0.34 Fe 0.33 Mn 0.33 O 2 As a positive electrode active material, the assembled sodium ion pouch cell achieved an initial specific capacity of about 106.8mA h/g in the voltage interval of 2-4V. After 100 cycles of circulation at 25/45/60/100 ℃, the specific discharge capacity of the material is 95.5/85.3/80.3/71.15mA h/g respectively. This means that Na having 3D frame structure is not introduced 5 B 4 The compound significantly reduces the performance of the battery.
The test results of other examples are shown in table 2.
TABLE 2
| Molecular formula | Current density 0.1C, put Specific electrical capacity (mA h/g) | First library Rending effect Rate% | Cycling at 25 DEG C Specific volume of 100 circles Quantity (mA h- g) | Circulation at 45 DEG C Specific volume of 100 circles Quantity (mA h- g) | Circulation at 60 DEG C Specific volume of 100 circles Quantity (mA h- g) | Circulation at 100 DEG C Ring 100 circles Specific capacity of (mA h/g) | |
| Example 1 | Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 140.5 | 86.1 | 133.6 | 129.2 | 120.4 | 107.98 |
| Example 2 | Na 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 126.2 | 81.6 | 115.8 | 110.5 | 100.3 | 91.4 |
| Comparative example 1 | NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 106.8 | 71.4 | 95.5 | 85.3 | 77.3 | 71.15 |
| Example 3 | K 5 B 4 //NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 128.4 | 85.6 | 120.5 | 110.4 | 100.5 | 91.66 |
| Example 4 | K 5 B 4 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 120.65 | 80.8 | 118.66 | 108.3 | 97.8 | 90.32 |
| Example 5 | Li 5 B 4 //NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 121.4 | 81.5 | 119.2 | 109.5 | 99.3 | 91.5 |
| Example 6 | K 3 B 2 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 120.9 | 80.99 | 118.9 | 108.9 | 98.0 | 90.5 |
| Example 7 | Na 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 121.5 | 81.3 | 119.4 | 109.6 | 99.2 | 91.3 |
| Example 8 | Na 3 B 2 /NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 121.1 | 81.0 | 119.1 | 109.2 | 99.0 | 90.8 |
| Example 9 | K 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 119.8 | 79.9 | 118.0 | 105.5 | 96.3 | 89.4 |
| Example 10 | Li 2 B/NaNi 0.34 Fe 0.33 Mn 0.33 O 2 | 115.5 | 78.8 | 110.3 | 100.8 | 92.3 | 85.7 |
From the results in table 2, it can be seen that: in comparative example 1, pure layered oxide NaNi was used 0.34 Fe 0.33 Mn 0.33 O 2 As the positive electrode material, the obtained sodium ion battery has the lowest specific discharge capacity, initial coulombic efficiency and specific volume after 100 circles of circulation at different temperatures.
In example 1, in the layered oxide NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Na with 3D frame structure 5 B 4 After the compound, the good mechanical and thermal stability of the compound improves the O3 phase layered oxide NaNi 0.34 Fe 0.33 Mn 0.33 O 2 And Na 5 B 4 The presence of alkali Na in the compound produced a "pre-sodium" effect, which increased the energy density of the material, and therefore compared to comparative example 1, the specific discharge capacity, the first coulombic efficiency and the specific capacity after 100 cycles at different temperatures of the battery of example 1 were all significantly improved.
Also, in examples 2 to 10, since M having a 3D frame structure is introduced x B y After the compound, the specific discharge capacity, the first coulombic efficiency and the specific capacity after 100 circles of circulation at different temperatures of the battery are compared with the pure lamellar oxide NaNi 0.34 Fe 0.33 Mn 0.33 O 2 Further improvements are provided.
In summary, the present invention introduces M with 3D framework structure into layered oxide x B y The compound can greatly improve the cycle performance of the battery and has good performanceThe initial coulombic efficiency of the full cell loss is compensated.
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 (10)
1. A layered oxide composite material of a sodium ion battery is characterized in that the molecular formula of the layered oxide composite material of the sodium ion battery is M x B y /NaNi a Fe b Mn c O 2 Wherein: m is an alkali metal element, x is more than or equal to 1 and y is more than or equal to 9; 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
2. The layered oxide composite of a sodium ion battery of claim 1, wherein the D50 particle size of the layered oxide composite of a sodium ion battery is 0.01-25.5 μm;
and/or the specific surface area of the sodium ion battery layered oxide composite material is 0.01-47.4 m 2 /g；
And/or, the water content of the sodium ion battery layered oxide composite material is 0.01% -1.25%.
3. The preparation method of the layered oxide composite material of the sodium ion battery is characterized by comprising the following steps of:
s1, mixing alkali metal M powder and boron powder in vacuum or inert atmosphere, and performing vacuum hot extrusion to obtain M x B y A compound;
s2. M x B y Compounds, naNi a Fe b Mn c O 2 After mixing the powder, carrying out hot extrusion to obtain the layered oxide composite material of the sodium ion battery;
in the step S1, x is more than or equal to 1 and y is more than or equal to 9;
in step S2, 0.ltoreq.a, b, c.ltoreq.1, and a+b+c=1.
4. The method for preparing a layered oxide composite material for sodium ion battery according to claim 3, wherein in step S1, the molar ratio of the alkali metal M powder to the boron powder is 1-10:1-6;
and/or the temperature of the vacuum hot extrusion is 1000-1500 ℃, the pressure is 10-500 Mpa, and the heat preservation time is 0.5-6 h.
5. The method for preparing a layered oxide composite material for sodium ion battery according to claim 3, wherein in step S2, the hot extrusion temperature is 700-1200 ℃, the pressure is 10-500 Mpa, and the heat preservation time is 0.5-48 h;
and/or the heating rate of the hot extrusion is 0.01-10 ℃/min.
6. The method for preparing a layered oxide composite material for sodium ion battery as claimed in claim 3, wherein in step S2, the NaNi is a Fe b Mn c O 2 The preparation method of the powder comprises the following steps:
a. mixing sodium salt and metal salt, and stirring uniformly; the metal salt comprises at least one of nickel salt, iron salt and manganese salt;
b. sintering the mixture obtained in the step a to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein in the step a, the sodium salt comprises at least one of sodium chloride, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfide, sodium sulfite, sodium bisulphite, sodium nitrite, sodium chlorate, sodium ferrate, sodium fluoride, sodium bromide and sodium iodide;
and/or the nickel salt comprises at least one of nickel oxide, nickel sulfate, nickel chloride, nickel sulfamate, nickel bromide and nickel carbonyl;
and/or the ferric salt comprises at least one of ferrous oxide, ferric sulfate, ferric chloride, ferric nitrate and ferrous oxalate;
and/or the manganese salt comprises at least one of manganese oxide, potassium permanganate and potassium manganate;
and/or the molar ratio of the sodium salt to the metal salt is 0.05-1.25:0.01-1.
7. The method for preparing a layered oxide composite material for sodium ion battery as claimed in claim 3, wherein in step S2, the NaNi is a Fe b Mn c O 2 The preparation method of the powder comprises the following steps:
c. mixing sodium salt with precursor salt, and stirring uniformly;
d. c, sintering the mixture obtained in the step c to obtain the NaNi a Fe b Mn c O 2 A powder;
wherein the sodium salt comprises at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate;
and/or the precursor salt comprises at least one of nickel oxide, manganese oxide, iron oxide, nickel iron oxide, manganese iron oxide, nickel manganese oxide, nickel iron manganese oxide, nickel hydroxide, iron hydroxide, manganese hydroxide, nickel iron hydroxide, manganese iron hydroxide, nickel manganese hydroxide and nickel iron manganese hydroxide;
and/or the molar ratio of the sodium salt to the precursor salt is 0.01-1.25:0.01-1.
8. The method for preparing a layered oxide composite material for sodium ion battery according to claim 6 or 7, wherein in steps b and d: the sintering temperature is 800-1200 ℃, and the sintering time is 0.5-48 h;
and/or the temperature rising rate of the sintering is 0.01-10 ℃/min.
9. A positive electrode sheet comprising the layered oxide composite material for a sodium ion battery according to claim 1 or 2 or the layered oxide composite material for a sodium ion battery prepared by the method according to any one of claims 3 to 8.
10. A sodium ion battery comprising the positive electrode sheet of claim 9.
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