CN115810737A - Sodium ion battery positive electrode material, preparation method, battery and electric equipment - Google Patents
Sodium ion battery positive electrode material, preparation method, battery and electric equipment Download PDFInfo
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Abstract
The application discloses a sodium ion battery positive electrode material, a preparation method, a battery and electric equipment. The positive electrode material of the present application includes Na 4 Fe 3‑x M x (PO 4 ) 2 P 2 O 7 C, wherein X is more than or equal to 0.05 and less than or equal to 1.0; the mass percentage of C in the anode material is as follows: 1-10%, M element selected from one or more of Mn, ni, co, al and Ti, and D of the positive electrode material V50 Is 2 to 16 μm. The preparation method comprises the following steps: preparing a first solution: the first solution comprises a carbon source; preparing a second solution: the second solution includes M element; preparing a third solution: the third solution comprises a sodium source and an iron source; the prepared first solutionAnd carrying out spray drying on the second solution and the third solution to obtain a precursor, and sintering the precursor to obtain the anode material. The positive electrode material of the sodium-ion battery is coated with Na through carbon 4 Fe 3‑x M x (PO 4 ) 2 P 2 O 7 And the particle size distribution of the anode material is optimized, and the cycle performance of the anode material is improved.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a sodium-ion battery positive electrode material, a preparation method, a battery and electric equipment.
Background
Polyanionic compounds have received much attention because of their high electrode potential, strong structural framework, good thermal stability and fast kinetics of sodium ion deintercalation. Based on Fe 2+ /Fe 3+ The sodium-iron-based polyanion compound has higher working voltage and discharge specific capacity and higher energy density in general. In particular to a sodium iron based pyrophosphate material, which has three-dimensional sodium ion diffusion channels in the structure and has excellent electrode dynamics. Such as layered Na 3 Fe 2 (P 2 O 7 )PO 4 The lithium ion battery positive electrode material has the advantages of a two-dimensional sodium ion migration channel, high theoretical specific capacity, small structural change during oxidation-reduction reaction, high safety, high working voltage and the like, and the excellent performances enable the lithium ion battery positive electrode material to have great development potential. However, na 3 Fe 2 (P 2 O 7 )PO 4 The low electronic conductivity of the material severely limits its electrochemical performance. In the existing modification report, the nano-modification of the carbon-coated combined particles is to increase Na 3 Fe 2 (P 2 O 7 )PO 4 The electrochemical performance is simpler and more effective, but the carbon is coated with Na 3 Fe 2 (P 2 O 7 )PO 4 The carbon coating is used for improving the conductivity of the material, the capacity and the average voltage ratio of the material are low, and the capacity and the average voltage of the material cannot be improved by only coating the carbon.
Disclosure of Invention
The application aims to provide a sodium-ion battery positive electrode material, a preparation method, a battery and electric equipment. The positive electrode material of the sodium-ion battery is coated with Na through carbon 4 Fe 3-x M x (PO 4 ) 2 P 2 O 7 And the particle size distribution of the anode material is optimized, and the cycle performance of the anode material is improved.
The embodiment of the application provides a positive electrode material of a sodium-ion battery, wherein the positive electrode material comprises Na 4 Fe 3-x M x (PO 4 ) 2 P 2 O 7 C, wherein X is more than or equal to 0.05 and less than or equal to 1.0; the mass percentage of C in the anode material is as follows: 1-10%, M element selected from one or more of Mn, ni, co, al and Ti, and D of the positive electrode material V50 2 to 16 μm.
In some embodiments, the M element is a gradient distribution.
In some embodiments, the C is distributed in a gradient.
In some embodiments, the precursor for preparing the cathode material is a mixture of iron source/sodium source/metal salt/carbon source,
the precursor and the cathode material satisfy the following conditions: 5 is less than or equal to (S/S + T/T) \ 65121while W/W is less than or equal to 20, wherein W is D of the precursor V50 In μm; s is the specific surface area of the precursor and has the unit of m 2 (ii)/g; t is the tap density of the precursor, and the unit is g/cm 3 W is D of the positive electrode material V50 In units of μm; s is the specific surface area of the positive electrode material and has a unit of m 2 (ii)/g; t is the tap density of the anode material and has a unit of g/cm 3 。
In some embodiments of the present invention, the,
3.0≤W≤20；
2≤w≤16；
5≤S≤9；
6≤s≤15；
1.4≤T≤1.8；
1.2≤t≤2.0。
the embodiment of the application further provides a preparation method of the sodium-ion battery positive electrode material, which comprises the following steps:
preparing a first solution: the first solution comprises a carbon source;
preparing a second solution: the second solution comprises an M element;
preparing a third solution: the third solution comprises a sodium source and an iron source;
spray drying the prepared first solution, second solution and third solution to obtain a precursor, and sintering the precursor to obtain the anode material;
the parameters of the spray drying satisfy:
2≤F﹡f﹡M/H≤10；
0.2≤(D﹡d+E﹡e)/(F﹡f)≤4；
wherein D is the solid content of the first solution in g/L, D is the feed rate of the first solution in mL/min, E is the solid content of the second solution in g/L, E is the feed rate of the second solution in mL/min, F is the solid content of the third solution in g/L, F is the feed rate of the third solution in mL/min, M is the spray drying pressure in MPa, H is the spray drying fan frequency in HZ.
In some embodiments, 5 ≦ D ≦ 10; d is more than or equal to 1 and less than or equal to 10.
In some embodiments, 20 ≦ E ≦ 150; e is more than or equal to 2 and less than or equal to 14.
In some embodiments, 100 ≦ F ≦ 600; f is more than or equal to 2 and less than or equal to 50.
In some embodiments, 0.1. Ltoreq. M.ltoreq.0.5; h is more than or equal to 30 and less than or equal to 55.
In some embodiments, the first solution flows into a second solution, resulting in a first mixed solution;
and enabling the first mixed solution to flow into the third solution to obtain a second mixed solution, and performing spray drying on the second mixed solution.
In some embodiments, the precursor and the cathode material satisfy: 5 to less than or equal to (S/S + T/T) \ 65121while W/W is less than or equal to 20, wherein W is D of the precursor V50 In μm; s is the specific surface area of the precursor and has the unit of m 2 (iv) g; t is the tap density of the precursor, and the unit is g/cm 3 W is D of the positive electrode material V50 In μm; s is the specific surface area of the positive electrode material and has a unit of m 2 (iv) g; t is the tap density of the anode material and has a unit of g/cm 3 。
In some embodiments, the sintering comprises a first sintering and a second sintering; the temperature of the first sintering is 200-400 ℃, and the time of the first sintering is 1-3 h; the temperature of the second sintering is 500-600 ℃, and the time of the second sintering is 8-15 h.
Correspondingly, the embodiment of the application further provides a battery, which comprises the positive electrode material of the sodium-ion battery or the positive electrode material of the sodium-ion battery prepared by the preparation method.
Correspondingly, the embodiment of the application further provides an electric device which comprises the battery. The beneficial effect of this application lies in: the application provides a positive electrode material of a sodium-ion battery, which comprises Na 4 Fe 3-x M x (PO 4 ) 2 P 2 O 7 C, wherein X is more than or equal to 0.05 and less than or equal to 1.0; the mass percentage of C in the anode material is as follows: 1-10%, M element is selected from one or more of Mn, ni, co, al and Ti, and D of the positive electrode material V50 2 to 16 μm. Coating Na by C material 4 Fe 3- x M x (PO 4 ) 2 P 2 O 7 On one hand, the Taylor effect of the doped elements can be inhibited, the conductivity of the positive electrode material can be improved, and the capacity of the positive electrode material can be improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of a method of preparation of the present application;
fig. 2 is an EDSX spectrum of the cathode material prepared in example 1;
fig. 3 is a polished view of SEM scanning of the cathode material prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. In addition, in the description of the present application, the term "including" means "including but not limited to". The terms first, second, third and the like are used merely as labels, and do not impose numerical requirements or an order of establishment. Various embodiments of the present application may exist in a range of versions; it is to be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the application; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within a range of numbers, such as 1, 2, 3, 4, 5, and 6, for example, regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the range so indicated.
In order to solve the problems of low capacity, low average voltage and poor conductivity of the sodium iron phosphate composite cathode material, the embodiments of the present applicationA positive electrode material of sodium-ion battery is provided, the positive electrode material includes Na 4 Fe 3-x M x (PO 4 ) 2 P 2 O 7 C, wherein X is more than or equal to 0.05 and less than or equal to 1.0; the mass percentage of C in the anode material is as follows: 1-10%, M element selected from one or more of Mn, ni, co, al and Ti, and D of positive electrode material V50 2 to 16 μm.
Coating Na by C material 4 Fe 3-x M x (PO 4 ) 2 P 2 O 7 On one hand, the Taylor effect of the doped elements can be inhibited, the conductivity of the positive electrode material can be improved, and the capacity of the positive electrode material can be improved. The application further defines the mass percentage of the C in the positive electrode material, in the range, the conductivity and the capacity of the positive electrode material are both improved, when the mass fraction of the C is too high, the specific capacity of the material is reduced, and when the mass fraction of the C is too low, the electronic conductivity of the material is low, and the activity of the material is not enough.
In some embodiments, the particle size D of the cathode material of the present application V50 Is any value or any two value range of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 and 16.
In some embodiments, the present application further optimizes the particle size of the cathode material, the cathode material particle size D of the present application V50 Is 2-8 μm.
The particle size of the cathode material is within the range, the high material capacity, the excellent cycle performance and the excellent rate performance can be realized, when the particle size of the cathode material is lower than 2 micrometers, the cycle performance of the material is reduced, the gas generation risk of the battery core is caused, and when the particle size of the cathode material is higher than 8 micrometers, the material capacity is not expected.
In some implementations, the M element is a gradient distribution.
This application passes through the gradient doping of M element in positive electrode material, can improve positive electrode material's discharge voltage on the one hand, and the ginger taylor effect of some M elements can be avoided to the on the other hand.
In some embodiments, the M element is a Mn element.
In some implementations, C is distributed in a gradient.
The carbon material and the anode material form gradient compounding, so that the conductivity of the anode material is improved, the compaction density of the anode material can also be improved, the energy density and the rate capability of the anode material are further improved, and the Taylor effect of manganese can be inhibited.
In some implementations, the precursor for preparing the positive electrode material includes an iron source, a sodium source, a metal salt, and a carbon source;
the precursor and the cathode material meet the following conditions: 5 to less than or equal to (S/S + T/T) \ 65121while W/W is less than or equal to 20, wherein W is D of a precursor V50 In units of μm; s is the specific surface area of the precursor and has the unit of m 2 (iv) g; t is the tap density of the precursor, and the unit is g/cm 3 W is D of a positive electrode material V50 In μm; s is the specific surface area of the anode material and has a unit of m 2 (ii)/g; t is the tap density of the anode material and has a unit of g/cm 3 。
In some embodiments, the value of (S/S + T/T) \65121W/W is: 5. 6, 6.22, 7, 8, 8.68, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, or a range of any two values.
In some embodiments, 3 ≦ W ≦ 20.
In some embodiments, W takes on the value: 3. 4, 5, 6, 7, 8, 8.2, 9, 10, 10.2, 11, 11.3, 12, 13, 14, 15, 15.2, 16, 17, 18, 19, 19.3, 20, or a range of any two values.
In some embodiments, 2 ≦ w ≦ 16.
In some embodiments, w takes on the value: 2. 2.2, 2.3, 3, 3.2, 4, 5, 5.3, 6, 6.3, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, or a range of any two values.
In some embodiments, 5 ≦ S ≦ 9.
In some embodiments, S takes on the values: 5. 6, 6.2, 6.3, 7, 8, 8.3, 8.9, 9, or a range of any two values.
In some embodiments, 6 ≦ s ≦ 15.
In some embodiments, s takes on the value: 6. any value or range of any two values from 6.1, 7, 8, 8.1, 9, 10, 11, 12, 13, 14, 15.
In some embodiments, 1.4 ≦ T ≦ 1.8.
In some embodiments, T has a value of any one of 1.4, 1.6, 1.8, or any combination thereof.
In some embodiments, 1.2 ≦ t ≦ 2.0.
In some embodiments, any value or range of any two of 1.2, 1.5, 1.65, 1.7, 1.72, 1.75, 1.8, 1.82, 1.9, 2.0.
The application further controls and controls the specific surface area, tap density and D of the anode material and the precursor thereof V50 Particle size while establishing specific surface area, tap density and material D between the positive electrode material and its precursor V50 The particle size relationship improves the cycle performance and the compaction density of the anode material.
The embodiment of the application provides a preparation method of a sodium-ion battery cathode material, which comprises the following steps:
preparing a first solution: the first solution comprises a carbon source;
preparing a second solution: the second solution includes M element;
preparing a third solution: the third solution comprises a sodium source and an iron source;
spray drying the prepared first solution, second solution and third solution to obtain a precursor, and sintering the precursor to obtain a positive electrode material;
the parameters of the spray drying satisfy:
2≤F﹡f﹡M/H≤10；
0.2≤(D﹡d+E﹡e)/(F﹡f)≤4；
wherein D is the solid content of the first solution in g/L, D is the feeding speed of the first solution in mL/min, E is the solid content of the second solution in g/L, E is the feeding speed of the second solution in mL/min, F is the solid content of the third solution in g/L, F is the feeding speed of the third solution in mL/min, M is the pressure of spray drying in MPa, H is the fan frequency of spray drying in HZ.
In some embodiments, F \65121, F \65121andM/H have the values: 2. 2.69, 3, 3.08, 3.33, 4, 4.8, 5, 6, 7, 8, 9, 10 or a range of any two values.
In some embodiments, the values of (D \65121ld + E \65121e)/(F \65121f) are: 0.2, 0.3, 0.34, 0.39, 0.4, 0.42, 0.43, 0.44, 0.45, 0.5, 0.51, 0.57, 0.6, 0.61, 0.7, 0.8, 0.9, 1, 2, 3, 4, or a range of any two values.
The method can control the content of the doping element and the content of carbon by controlling the solid content and the feeding speed of different solutions, so that the gradient concentration distribution of the manganese element can be regulated and controlled.
Further, the solid content of the solution at the feeding speed, the spraying pressure and the fan frequency are controlled, so that the shape of the spray-dried material can be controlled to be good solid spheres, and the material has proper granularity, specific surface area and tap density.
In some embodiments, 5 ≦ D ≦ 10; d is more than or equal to 1 and less than or equal to 10. The solid content of the first solution and the feeding speed of the first solution are controlled within the range, so that a carbon source can be well and uniformly dispersed in a gradient manner in a spherical material, and the excellent electronic conductivity is obtained.
In some embodiments, D has a value of any one of 5, 6, 7, 8, 8.2, 9, 10, or a range of any two values.
In some embodiments, d has a value of any one of 1, 2, 3, 4, 4.2, 5, 6, 7, 8, 9, 10, or a range of any two values.
In some embodiments, 20 ≦ E ≦ 150; e is more than or equal to 2 and less than or equal to 14. The solid content and the feeding speed of the second solution are controlled within the range, and gradient elements can be well doped into the cathode material without damaging the original particles and the appearance of the cathode material.
In some embodiments, E takes on the values: 20. 30, 40, 45, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, or a range of any two values.
In some embodiments, e takes the value: 2.3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or a range of any two of them.
In some embodiments, 100 ≦ F ≦ 600; f is more than or equal to 2 and less than or equal to 50. The solid content and the feeding speed of the third solution are controlled within the range, and the particle morphology with better sphericity can be obtained in spraying.
In some embodiments, F has a value of any one of 100, 200, 300, 350, 400, 500, 600, or a range of any two values.
In some embodiments, f has a value of any one of 2, 3, 4, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, or a range of any two values.
In some embodiments, 0.1 ≦ M ≦ 0.5; h is more than or equal to 30 and less than or equal to 55. The present application controls the eye and fan frequency of spray drying within this range, allowing superior spray dried precursor materials to be obtained in spray drying.
In some embodiments, M is any of 0.1, 0.2, 0.3, 0.4, 0.5, or a range of any two values.
In some embodiments, H has a value of any one or a range of any two of 30, 35, 38, 40, 45, 50, 52, 55.
In some embodiments, the carbon source is selected from one or more of acetylene black, graphene, carbon nanotubes, glucose, super P, and conductive carbon black.
In some embodiments, the M element is selected from one or more of manganese sulfate, manganese oxalate, manganese acetate, manganese nitrate, manganese chloride, nickel sulfate, nickel acetate, and nickel nitrate.
In some embodiments, the sodium source is selected from one or more of monosodium phosphate, trisodium phosphate, sodium carbonate, sodium bicarbonate, and disodium phosphate.
In some embodiments, the iron source is selected from one or more of iron phosphate, iron nitrate, iron acetate, iron oxalate, and iron sulfate.
In some embodiments, the first solution flows into the second solution, resulting in a first mixed solution;
and allowing the first mixed solution to flow into the third solution to obtain a second mixed solution, and performing spray drying on the second mixed solution.
In some embodiments, the precursor and the cathode material satisfy: 5 is less than or equal to (S/S + T/T) \ 65121while W/W is less than or equal to 20, wherein W is D of the precursor V50 In units of μm; s is the specific surface area of the precursor and has the unit of m 2 (ii)/g; t is the tap density of the precursor, and the unit is g/cm 3 W is D of the positive electrode material V50 In units of μm; s is the specific surface area of the cathode material and has a unit of m 2 (iv) g; t is the tap density of the anode material and has a unit of g/cm 3 。
The specific surface area, tap density and material D of the anode material and the precursor thereof are regulated and controlled 50 Particle size while establishing specific surface area, tap density and material D between the positive electrode material and its precursor 50 The particle size relationship improves the cycle performance and the compaction density of the anode material.
In some embodiments, sintering comprises a first sintering and a second sintering.
In some embodiments, the temperature of the first sintering is 200-400 ℃ and the time of the first sintering is 1-3 h.
In some embodiments, the temperature (° c) of the first sintering is any of 200, 250, 300, 350, 400, or a range of any two.
In some embodiments, the time (h) for the first sintering is any value or range of any two values of 1, 1.5, 2, 2.5, 3.
In some embodiments, the temperature of the second sintering is 500-600 ℃, and the time of the second sintering is 8-15 h.
In some embodiments, the temperature (° c) of the second sintering is any of 500, 550, 600, or a range of any two.
In some embodiments, the time (h) for the second sintering is any value or range of any two values from 8, 9, 10, 11, 12, 13, 14, 15.
In some embodiments, the method of making the sodium-ion battery positive electrode material of the present application is made by:
preparing a first solution: the first solution contains a carbon slurry;
preparing a second solution: the second solution contains manganese acetate;
preparing a third solution: the third solution contains sodium dihydrogen phosphate, iron phosphate and citric acid;
performing spray drying on the first solution, the second solution and the third solution, wherein the first solution flows into the second solution, the second solution containing the first solution flows into the third solution, and the obtained mixed solution is directly subjected to spray drying;
sintering the material after spray drying;
and grinding and sieving the sintered material to obtain the cathode material.
Embodiments of the present application provide a battery including a sodium ion battery positive electrode material.
Specifically, the battery of this application includes positive pole piece, and positive pole piece includes the anodal mass flow body and sets up the anodal active material layer on the anodal mass flow body, and the anodal active material layer includes foretell sodium ion battery cathode material.
In specific implementation, the positive electrode material of the sodium-ion battery, the conductive agent, the binder and the solvent are uniformly stirred, and the positive electrode plate is prepared through the working procedures of sieving, coating, rolling, slitting, cutting and the like.
Specifically, the kind of the conductive agent is not limited, and any known conductive agent can be used. Examples of conductive agents may include, but are not limited to, one or more of the following: carbon materials such as natural graphite, artificial graphite, super P conductive carbon black, acetylene black, needle coke, carbon nanotubes, graphene, and the like. The positive electrode conductive agents may be used alone or in any combination.
The type of binder used in the production of the positive electrode active material layer is not particularly limited, and in the case of the coating method, it is sufficient if it is a material that is soluble or dispersible in the liquid medium used in the production of the electrode. Examples of binders may include, but are not limited to, one or more of the following: polyethylene, polypropylene, polyvinylidene fluoride (PVDF), polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and the like. The above binders may be used alone or in any combination thereof.
The type of solvent used to form the positive electrode slurry is not limited as long as it can dissolve or disperse the positive electrode active material, the conductive agent, and the binder. Examples of the solvent used for forming the positive electrode slurry may include any one of an aqueous solvent and an organic solvent. Examples of aqueous media may include, but are not limited to: water, mixed media of alcohol and water, and the like. Examples of organic based media may include, but are not limited to: hexane, benzene, toluene, xylene, pyridine, acetone, tetrahydrofuran (THF), N-methylpyrrolidone (NMP), and the like.
Specifically, the battery comprises a positive pole piece, a negative pole piece, an isolation film and electrolyte, wherein the positive pole piece is the positive pole piece. In specific implementation, the positive pole piece, the negative pole piece, the isolating membrane, the electrolyte and the like are assembled into the sodium ion battery, wherein the negative pole piece is a metal sodium piece.
Embodiments of the present application also provide an electric device including the above battery.
In some embodiments, the powered devices of the present application include, but are not limited to: the power supply comprises a standby power supply, a motor, an electric automobile, an electric motorcycle, a power-assisted bicycle, a bicycle, an electric tool, a household large-scale storage battery and the like.
Example 1
Preparing carbon slurry containing 6g/L of acetylene black, homogenizing for 2 hours under the condition of 1000Pa by using high-pressure microjet, and uniformly dispersing the carbon material to be marked as a first solution;
preparing 100g/L of manganese acetate aqueous solution and recording as a second solution;
the method comprises the following steps of proportioning sodium dihydrogen phosphate and iron phosphate according to a molar ratio of 4.9, wherein the solution concentration is 300g/L, and the manganese content in the solution B is sodium dihydrogen phosphate: manganese acetate was 4: iron phosphate: manganese acetate was 4.
The inlet pipe is connected: connecting the first solution and the second solution with a pipe, placing the first solution into the feed inlet A, placing the second solution into the discharge outlet B, connecting the second solution and the third solution with a pipe, placing the second solution into the feed inlet B, placing the third solution into the discharge outlet C, and connecting the third solution with a spray dryer, as shown in figure 1.
And simultaneously feeding the prepared three solutions for spray drying, wherein the solution A flows into the solution B, the solution B flows into the solution C, and the solution C is subjected to spray drying through a spray dryer.
Calcining the spray-dried material in a tubular furnace at 300 ℃ for 2h and 550 ℃ for 10h, wherein the heating rate is 1 ℃/min and the nitrogen atmosphere is 1L/min;
sieving the calcined material by a 400-mesh sieve, and then packaging to obtain a finished product sample Na 4 Fe 2.9 Mn 0.1 (PO 4 ) 2 P 2 O 7 /C。
Example 2 to example 4: the preparation method is the same as that of example 1, except that the C element and Na are controlled by adjusting the addition ratio of the C source and the preparation parameters 4 Fe 3-x M x (PO 4 ) 2 P 2 O 7 The mass ratio of (a).
Example 5 to example 6: the preparation method is the same as example 1, except that Na is further adjusted by adjusting the mass ratio of the iron source to the Mn source and the preparation parameters 4 Fe 3-x M x (PO 4 ) 2 P 2 O 7 The composition of (a).
Example 7: the preparation method is the same as that of example 1, except that preparation parameters are adjusted, the first solution is directly added to the third solution and uniformly stirred to serve as a fourth solution, the second solution and the fourth solution are connected, the second solution flows into the fourth solution, and the fourth solution is spray-dried by a spray dryer.
Example 8: the preparation method is the same as that of example 1, except that preparation parameters are adjusted, the second solution is directly added to the third solution and uniformly stirred to serve as a fifth solution, the first solution and the fifth solution are connected, the first solution flows into the fifth solution, and the fifth solution is spray-dried by a spray dryer.
Examples 9 to 11: the preparation method is the same as example 1, except that the numerical values of F \65121f \65121andM/H are adjusted by adjusting the preparation parameters of spray drying.
Example 12 to example 14: the preparation method is the same as example 1, except that the numerical value of (D \65121; D + E \65121; E)/(F \65121f) is further adjusted by adjusting the preparation parameters of spray drying.
Example 15 to example 17: the preparation method is the same as that of the embodiment 1, and is different in that the values of (S/S + T/T) \65121and W/W are controlled by adjusting the parameters of spray drying and further adjusting the parameters of the precursor.
Example 18 to example 20: the preparation method is the same as that of example 1, except that the Dv of the precursor is controlled by adjusting the solid content and the material speed of the solution 50 And further controlling the Dv of the positive electrode material 50 。
Comparative example 1: the preparation method is the same as example 1, except that the preparation parameters are adjusted and the material C is not coated.
Comparative example 2: the preparation method is the same as example 1, except that the preparation parameters are adjusted, and the coating amount of the material C is 15%.
Comparative example 3: the preparation method is the same as example 1, except that the coating amount of the material C is 0.2% by adjusting the preparation parameters.
The battery assembling method comprises the following steps: the positive pole piece comprises: the materials prepared in examples 1 to 20 or comparative examples 1 to 3, conductive carbon black and polyvinylidene fluoride (PVDF) as a binder were mixed at a mass ratio of 90. The negative electrode adopts a metal sodium sheet, the diaphragm is a polypropylene porous membrane, and the electrolyte is NaPF of lmol/L 6 EC + DEC + DMC (EC: DEC: DMC = 1.
Initial specific capacity test conditions: 0.1C,1.5V-4.05V test; note: 1C =129mA/g.
Multiplying power performance test conditions: 0.1C for 5 weeks, 0.2C for 5 weeks, 0.5C for 5 weeks, 1C for 5 weeks, 2C for 5 weeks, 3C for 5 weeks.
Cycle performance test conditions: 0.2C, and testing at normal temperature for 180 weeks.
TABLE 1
TABLE 2
From the results in Table 2, it can be seen that when the carbon source is not added or is added less, the electron conductivity of the obtained material is obtained, and the capacity of the material is extremely low, while when the carbon source is added too much, the electron conductivity of the material is improved, but the gram capacity of the obtained material is low, the capacity exertion of the material is limited, and all the parameters are within the specified range, the obtained material has high capacity and excellent rate performance, while the capacity of the material outside the specified parameters is slightly inferior to the ideal material performance.
As can be seen from Table 2, by controlling the parameters of (1) < 2 > F </65121; F </65121; M/H < 10 >, (2) < 0.2 < D > 65121; D + E </65121; E)/(F </65121; F) < 4 > in the relational expressions, a positive electrode material with better performance can be obtained, and if the parameters are out of the range of a single parameter, the rate performance of the material is inferior to the material performance of both parameters, and if the parameters are not in the required ranges, the capacity, compaction and rate performance of the material are all sharply reduced.
TABLE 3
From the results in table 3, it can be seen that the parameters of the cathode material are further adjusted according to the performance parameters of the precursor, and the precursor and the cathode material maintain a certain relationship, so that the material has higher capacity and rate capability and better cycle performance.
In the foregoing embodiments, the descriptions of the respective embodiments have respective emphasis, and for parts that are not described in detail in a certain embodiment, reference may be made to related descriptions of other embodiments.
The positive electrode material, the preparation method, the battery and the electric device of the sodium-ion battery provided by the embodiment of the application are introduced in detail, a specific example is applied in the description to explain the principle and the implementation mode of the application, and the description of the embodiment is only used for helping to understand the method and the core idea of the application; meanwhile, for those skilled in the art, according to the idea of the present application, the specific implementation manner and the application scope may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present application.
Claims (10)
1. The positive electrode material of the sodium-ion battery is characterized by comprising Na 4 Fe 3-x M x (PO 4 ) 2 P 2 O 7 C, wherein X is more than or equal to 0.05 and less than or equal to 1.0; the mass percentage of C in the anode material is as follows: 1-10%, M element selected from one or more of Mn, ni, co, al and Ti, and D of the positive electrode material V50 Is 2 to 16 μm.
2. The positive electrode material for sodium-ion batteries according to claim 1, wherein said M element is distributed in a gradient manner; and/or the presence of a gas in the atmosphere,
the C is distributed in a gradient manner.
3. The positive electrode material for the sodium-ion battery according to claim 1, wherein precursors for preparing the positive electrode material include an iron source, a sodium source, a metal salt, and a carbon source;
the precursor and the cathode material satisfy the following conditions: 5 to less than or equal to (S/S + T/T) \ 65121while W/W is less than or equal to 20, wherein W is D of the precursor V50 In μm; s is the specific surface area of the precursor and has the unit of m 2 (ii)/g; t is the tap density of the precursor in g/cm 3 W is D of the positive electrode material V50 In μm; s is the specific surface area of the cathode material and has a unit of m 2 (iv) g; t is the tap density of the anode material and has a unit of g/cm 3 (ii) a And/or the presence of a gas in the gas,
3.0≤W≤20；
2≤w≤16；
5≤S≤9；
6≤s≤15；
1.4≤T≤1.8；
1.2≤t≤2.0。
4. the preparation method of the positive electrode material of the sodium-ion battery according to claim 1, characterized by comprising the following steps:
preparing a first solution: the first solution comprises a carbon source;
preparing a second solution: the second solution comprises an M element;
preparing a third solution: the third solution comprises a sodium source and an iron source;
and carrying out spray drying on the prepared first solution, the second solution and the third solution to obtain a precursor, and sintering the precursor to obtain the cathode material.
5. The method for preparing the positive electrode material of the sodium-ion battery according to claim 4, wherein the parameters of the spray drying satisfy:
2≤F﹡f﹡M/H≤10；
0.2≤(D﹡d+E﹡e)/(F﹡f)≤4；
wherein D is the solid content of the first solution in g/L, D is the feed rate of the first solution in mL/min, E is the solid content of the second solution in g/L, E is the feed rate of the second solution in mL/min, F is the solid content of the third solution in g/L, F is the feed rate of the third solution in mL/min, M is the spray drying pressure in MPa, H is the spray drying fan frequency in HZ; and/or the presence of a gas in the atmosphere,
d is more than or equal to 5 and less than or equal to 10; d is more than or equal to 1 and less than or equal to 10; and/or the presence of a gas in the gas,
e is more than or equal to 20 and less than or equal to 150; e is more than or equal to 2 and less than or equal to 14; and/or the presence of a gas in the atmosphere,
f is more than or equal to 100 and less than or equal to 600; f is more than or equal to 2 and less than or equal to 50; and/or the presence of a gas in the gas,
0.1≤M≤0.5；30≤H≤55。
6. the method for preparing the positive electrode material for sodium-ion batteries according to claim 4,
the first solution flows into the second solution to obtain a first mixed solution;
and enabling the first mixed solution to flow into the third solution to obtain a second mixed solution, and performing spray drying on the second mixed solution.
7. The method for preparing the positive electrode material of the sodium-ion battery according to claim 4, wherein the precursor and the positive electrode material satisfy the following conditions: 5 is less than or equal to (S/S + T/T) \ 65121while W/W is less than or equal to 20, wherein W is D of the precursor V50 In μm; s is the specific surface area of the precursor and has the unit of m 2 (ii)/g; t is the tap density of the precursor in g/cm 3 W is D of the positive electrode material V50 In μm; s is the specific surface area of the positive electrode material and has a unit of m 2 (iv) g; t is the tap density of the anode material and has a unit of g/cm 3 。
8. The method for preparing the positive electrode material for the sodium-ion battery according to claim 4, wherein the sintering comprises a first sintering and a second sintering; the temperature of the first sintering is 200-400 ℃, and the time of the first sintering is 1-3 h; the temperature of the second sintering is 500-600 ℃, and the time of the second sintering is 8-15 h.
9. A battery comprising the positive electrode material for sodium-ion batteries according to any one of claims 1 to 3 or the positive electrode material for sodium-ion batteries produced by the production method according to any one of claims 4 to 8.
10. An electrical device comprising the battery of claim 9.
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