CN117374212A - Positive electrode material, preparation method thereof and positive electrode plate - Google Patents

Positive electrode material, preparation method thereof and positive electrode plate Download PDF

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Publication number
CN117374212A
CN117374212A CN202311592510.8A CN202311592510A CN117374212A CN 117374212 A CN117374212 A CN 117374212A CN 202311592510 A CN202311592510 A CN 202311592510A CN 117374212 A CN117374212 A CN 117374212A
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positive electrode
layered oxide
electrode material
sintering
surface area
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程斯琪
陈森
王建鑫
戚兴国
李树军
唐堃
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Shanxi Huana Copper Energy Technology Co ltd
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Shanxi Huana Copper Energy Technology Co ltd
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
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    • 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
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    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • 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
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    • 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
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    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes

Abstract

The invention relates to the technical field of sodium batteries, in particular to a positive electrode material, a preparation method thereof and a positive electrode plate. The preparation method of the positive electrode material comprises the following steps: carrying out first sintering on the layered oxide and a sodium source at the temperature of T+/-20 ℃ to obtain the anode material; wherein t=850-td×100×t/s×β; TD is the tap density of the layered oxideIs expressed in g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the S is the value of the specific surface area of the layered oxide, and the unit of the specific surface area is m 2 /g; t is the value of the time of the first sintering, and the unit of time is h; beta is the mass ratio of Na element in the sodium source and Na element in the layered oxide. The invention improves the morphology of the material and improves the fluidity by sintering the layered oxide and regulating and controlling the sintering temperature.

Description

Positive electrode material, preparation method thereof and positive electrode plate
Technical Field
The invention relates to the technical field of sodium batteries, in particular to a positive electrode material, a preparation method thereof and a positive electrode plate.
Background
The sodium ion battery has the characteristics of high safety, abundant raw materials, low cost and the like, and becomes a research and development hot spot of the battery technology in recent years. The sodium ion battery can be applied to the fields of low-speed electric vehicles, energy storage devices and the like.
Among various positive electrode materials of sodium ion batteries, the layered oxide positive electrode material of the sodium ion battery has higher theoretical capacity. However, the sodium ion layered oxide positive electrode material is easy to form a large sheet shape after high-temperature sintering, the shape can lead to poor fluidity (P is less than 0.6) of the material, the transportation in the production process is difficult, and the compaction density of a pole piece prepared from the positive electrode material is low (< 3 g/cm) 3 ) Resulting in difficulty in increasing the energy density of the sodium ion battery. However, if high-temperature sintering is not performed, the material is difficult to phase, the agglomeration is serious, the morphology similar to single crystals is difficult to maintain, and the compaction density of a pole piece prepared from the positive electrode material is low (< 2.8 g/cm) 3 )。
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a method for preparing a positive electrode material, which improves the morphology of the material and improves the flowability of the material by sintering a layered oxide and controlling the sintering temperature.
The second object of the present invention is to provide a positive electrode material having a ball-like or olive-like morphology and excellent fluidity.
A third object of the present invention is to provide a positive electrode sheet having a high compacted density.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a preparation method of a positive electrode material, which comprises the following steps:
carrying out first sintering on the layered oxide and a sodium source at the temperature of T+/-20 ℃ to obtain the anode material;
wherein t=850-td×100×t/s×β; TD is the value of the tap density of the layered oxide, the unit of tap density is g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the S is the value of the specific surface area of the layered oxide, and the unit of the specific surface area is m 2 /g; t is the value of the time of the first sintering, and the unit of time is h; beta is the mass ratio of Na element in the sodium source and Na element in the layered oxide.
Further, β is 0.0001 to 0.02.
Further, at least one of the following features (1) to (3) is included;
(1) The layered oxide includes Na δ Cu y Ni z Fe s Mn t (OH) 2 ；0.9≤δ≤1.1，0.08≤y≤0.14，0.18≤z≤0.24，0.3≤s≤0.36，0.32≤t≤0.35，y+z+s+t＝1；
(2) The tap density of the layered oxide is 1-2 g/cm 3 ；
(3) The specific surface area of the layered oxide is 0.3-1 m 2 /g。
Further, the time of the first sintering is 8-24 hours.
Further, the preparation method of the layered oxide comprises the following steps:
and (3) performing second sintering on the sodium source and the nickel-copper-iron-manganese hydroxide to obtain the layered oxide.
Further, the chemical formula of the nickel-copper-iron-manganese hydroxide is Cu y Ni z Fe s Mn t (OH) 2 ；0.08≤y≤0.14，0.18≤z≤0.24，0.3≤s≤0.36，0.32≤t≤0.35，y+z+s+t＝1。
Further, at least one of the following features (1) to (3) is included;
(1) The particle size D50 of the nickel-copper-iron-manganese hydroxide is 4-10 mu m;
(2) The tap density of the nickel-copper-iron-manganese hydroxide is more than or equal to 1g/cm 3 ；
(3) The specific surface area of the nickel-copper-iron-manganese hydroxide is 10-30 m 2 /g。
Further, the second sintering includes: heat preservation is carried out for 8 to 24 hours at 950 to 1200 ℃.
The invention also provides a positive electrode material, which is prepared by adopting the preparation method of the positive electrode material.
The invention also provides a positive plate which comprises the positive electrode material.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the positive electrode material, the layered oxide is sintered, and the functional relation among the sodium supplementing amount beta, the sintering time T, the specific surface area S of the layered oxide, the tap density TD of the layered oxide and the sintering temperature T is regulated and controlled; the large-flake morphology of the layered oxide can be improved to be similar to a sphere or olive morphology, so that the flowability of the material is improved.
2. The positive electrode material has a ball-like or olive-like shape and excellent fluidity, and the dullness is more than or equal to 0.6.
3. The positive electrode material is used for preparing the positive electrode plate, and is beneficial to improving the compaction density of the positive electrode plate, so that the electrochemical performance of the sodium ion battery is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is an SEM image of the layered oxide of example 1 of the present invention.
Fig. 2 is an SEM image of the positive electrode material of example 1 of the present invention.
Fig. 3 is an SEM image of the positive electrode material of example 4 of the present invention.
Fig. 4 is an SEM image of the positive electrode material of comparative example 8 of the present invention.
Fig. 5 is an SEM image of the positive electrode material of comparative example 9 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In some embodiments of the present invention, a method for preparing a positive electrode material is provided, including the steps of:
carrying out first sintering on the layered oxide and a sodium source at the temperature of T+/-20 ℃ to obtain a positive electrode material;
wherein t=850-td×100×t/s×β; TD is the value of tap density of the layered oxide, the unit of tap density is g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the S is the value of the specific surface area of the layered oxide, and the unit of the specific surface area is m 2 /g; t is the value of the first sintering time, and the unit of time is h; beta is the mass ratio of Na element in the sodium source and Na element in the layered oxide.
In the invention, beta is the sodium supplementing amount, namely the mass ratio of Na element in a sodium source to Na element in the layered oxide in the first sintering process; in the invention, a small amount of sodium element is supplemented in the first sintering process.
According to the preparation method of the positive electrode material, the layered oxidation is sintered, and the functional relation among the sodium supplementing amount beta, the sintering time T, the specific surface area S of the layered oxide, the tap density TD of the layered oxide and the sintering temperature T is regulated and controlled; the temperature of the first sintering can be determined by the relational expression, the error is within +/-20 ℃, and the large-sheet morphology of the layered oxide can be improved to be of a sphere-like or olive-like morphology, so that the flowability of the material is improved.
The tap density of the layered oxide is high, after sodium is supplemented, the solid-phase reaction sodium source is difficult to diffuse into the interior, and the sodium supplementing amount is increased to relieve the problem of sodium deficiency caused by uneven mixing; the tap density of the layered oxide is low, the diffusion is rapid, and the sodium supplementing amount is reduced to relieve the sodium enrichment problem; the sodium supplementing amount is increased, and the sintering temperature can be reduced; the specific surface area of the layered oxide is high, the reactivity is high, the sintering temperature needs to be reduced, and the opposite is the case that the specific surface area of the layered oxide is low; to ensure the same sintering effect, increasing the sintering time period can suitably reduce the sintering temperature, and thus, td×100×t/s×β can characterize the ease of sintering.
In some embodiments of the invention, β is 0.0001 to 0.02; typically, but not by way of limitation, beta may be, for example, a range value of 0.0001, 0.0005, 0.001, 0.005, 0.01, 0.015, 0.02, or any two of the foregoing.
In some embodiments of the invention, the layered oxide comprises Na δ Cu y Ni z Fe s Mn t (OH) 2 ；0.9≤δ≤1.1，0.08≤y≤0.14，0.18≤z≤0.24，0.3≤s≤0.36，0.32≤t≤0.35，y+z+s+t＝1。
In some embodiments of the invention, the sodium source comprises NaOH, na 2 CO 3 、NaHCO 3 And NaNO 3 At least one of them. Preferably, the sodium source comprises Na 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the Sodium carbonate has a certain fluxing effect.
In some embodiments of the invention, the layered oxide has a tap density of 1 to 2g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Typically, but not by way of limitation, e.g. layered oxidesThe tap density of (C) may be 1g/cm 3 、1.2g/cm 3 、1.4g/cm 3 、1.6g/cm 3 、1.8g/cm 3 、2g/cm 3 Or a range value comprised of any two of these.
In some embodiments of the invention, the layered oxide has a specific surface area (BET) of 0.3 to 1m 2 /g; typical but non-limiting, for example, the specific surface area of the layered oxide may be 0.3m 2 /g、0.4m 2 /g、0.5m 2 /g、0.6m 2 /g、0.7m 2 /g、0.8m 2 /g、0.9m 2 /g、1m 2 /g or any two of them.
In some embodiments of the invention, the time for the first sintering is from 8 to 24 hours; typically, but not by way of limitation, the time for the first sintering is, for example, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or a range of values consisting of any two of these.
The sodium supplementing amount beta, the tap density and the specific surface area of the layered oxide and the first sintering time are in the ranges, so that the fluidity of the prepared positive electrode material is improved, and the compaction density and the cycle performance of the positive electrode plate are improved.
In some embodiments of the invention, the temperature of the first sintering is 500 to 850 ℃; typically, but not by way of limitation, the temperature of the first sintering may be, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, or a range of values consisting of any two thereof.
In some embodiments of the invention, the first sintering is performed under an oxygen-containing atmosphere; preferably, the oxygen-containing atmosphere is air or oxygen; more preferably, the rate of temperature rise during the first sintering is 1 to 10 ℃/min.
In some embodiments of the invention, a method of preparing a layered oxide comprises the steps of:
and (3) performing secondary sintering on the sodium source and the nickel-copper-iron-manganese hydroxide to obtain the layered oxide.
In some embodiments of the invention, the molar ratio δ of Na element to nickel copper iron manganese hydroxide in the sodium source is (0.9-1.1): 1, a step of; typically, but not by way of limitation, the molar ratio δ of Na element to nickel copper iron manganese hydroxide in the sodium source may be 0.9: 1. 0.92: 1. 0.94: 1. 0.96: 1. 0.98: 1. 1: 1. 1.2: 1. 1.4: 1. 1.6: 1. 1.8: 1.2:1 or any two thereof.
In some embodiments of the invention, the nickel copper iron manganese hydroxide has the formula Cu y Ni z Fe s Mn t (OH) 2 ；0.08≤y≤0.14，0.18≤z≤0.24，0.3≤s≤0.36，0.32≤t≤0.35，y+z+s+t＝1。
In some embodiments of the invention, the impurity element in the nickel copper iron manganese hydroxide includes at least one of Na, S, ca, mg, al, zn, co and Li; preferably, the contents of Na, S, ca, mg, al, zn, co and Li in the nickel-copper-iron-manganese hydroxide are each independently < 5000ppm.
In some embodiments of the invention, the nickel copper iron manganese hydroxide has a particle size D50 of 4 to 10 μm; typical, but non-limiting, particle size D50 of the nickel copper iron manganese hydroxide may be, for example, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm or a range of values consisting of any two of these.
In some embodiments of the invention, the tap density of the nickel-copper-iron-manganese hydroxide is greater than or equal to 1g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Preferably, the tap density of the nickel-copper-iron-manganese hydroxide is 1-2 g/cm 3 。
In some embodiments of the invention, the nickel copper iron manganese hydroxide has a specific surface area (BET) of 10 to 30m 2 /g; typical but non-limiting, for example, nickel copper iron manganese hydroxides may have a specific surface area of 10m 2 /g、15m 2 /g、20m 2 /g、25m 2 /g、30m 2 /g or any two of them.
In some embodiments of the invention, the second sintering comprises: heat preservation treatment is carried out for 8 to 24 hours at 950 to 1200 ℃; typically, but not by way of limitation, the temperature of the second sintering may be, for example, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, or a range of values consisting of any two thereof; the time of the second sintering may be 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or a range of values consisting of any two of these.
In some embodiments of the invention, the second sintering is performed under an oxygen-containing atmosphere; preferably, the oxygen-containing atmosphere is air or oxygen; more preferably, the rate of temperature increase during the second sintering is 1 to 10 ℃/min.
In some embodiments of the present invention, a positive electrode material is also provided, and the positive electrode material is prepared by using the preparation method of the positive electrode material.
In some embodiments of the invention, the dullness of the positive electrode material is greater than or equal to 0.6; preferably, the dullness of the positive electrode material is not less than 0.7.
In some embodiments of the invention, the positive electrode material has a ball-like or olive-like morphology; the appearance is more round, thereby being beneficial to improving the fluidity of the anode material.
In some embodiments of the present invention, a positive electrode material is also provided, and the positive electrode material is prepared by using the preparation method of the positive electrode material.
The positive electrode material is used for preparing the positive electrode plate, and is beneficial to improving the compaction density of the positive electrode plate.
In some embodiments of the invention, a sodium ion battery is provided, including the positive electrode sheet; the adoption of the positive plate is beneficial to improving the cycle performance of the sodium ion battery.
Further description will be provided below in connection with specific examples.
Example 1
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After being mixed at high speed, the mixture is heated to 1000 ℃ at a speed of 5 ℃/min under the air atmosphere and is heat-preserved for 15 hours to obtain the lamellar oxygenA chemical compound;
s2, layered oxide and 47.27g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 530 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 24 hours, and the mixture is crushed and sieved to obtain the anode material.
Example 2
The positive electrode material (Na 1.1 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.570kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 Tap density of 1.0g/cm 3 Specific surface area of 20m 2 After mixing at high speed, heating to 970 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 0.26g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 850 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 8 hours, and the mixture is crushed and sieved to obtain the anode material.
Example 3
The positive electrode material (Na 0.9 Cu 0.12 Mn 0.35 Ni 0.23 Fe 0.3 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.1kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.12 Mn 0.35 Ni 0.23 Fe 0.3 (OH) 2 Tap density of 2.4g/cm 3 Specific surface area of 10m 2 After mixing at high speed, heating to 1200 ℃ at a speed of 10 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 10.50g of Na 2 CO 3 Uniformly mixing (with purity of 99.68%), heating to 836 deg.C at a speed of 3 deg.C/min under air atmosphere, maintaining the temperature for 15 hr, pulverizing, and sieving to obtain the final productA polar material.
Example 4
The positive electrode material (Na 1.02 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.383kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 Tap density of 1.3g/cm 3 Specific surface area of 20m 2 After mixing at high speed, heating to 970 ℃ at a speed of 8 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 24 hours to obtain a layered oxide;
s2, layered oxide and 23.83g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 797 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and screened to obtain the anode material.
Example 5
The positive electrode material (Na 1.05 Cu 0.11 Mn 0.33 Ni 0.22 Fe 0.34 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.453kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.11 Mn 0.33 Ni 0.22 Fe 0.34 (OH) 2 Tap density of 1.8g/cm 3 Specific surface area of 20m 2 After mixing at high speed, heating to 1050 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 8 hours to obtain a layered oxide;
s2, layered oxide and 36.79g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 789 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation for 18 hours, and the mixture is crushed and screened to obtain the anode material.
Example 6
The positive electrode material (Na 0.95 Cu 0.14 Mn 0.32 Ni 0.18 Fe 0.36 O 2 ) Is prepared fromThe method comprises the following steps:
s1, 2.216kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.14 Mn 0.32 Ni 0.18 Fe 0.36 (OH) 2 Tap density of 2g/cm 3 Specific surface area of 15m 2 After mixing at high speed, heating to 1100 ℃ at a speed of 3 ℃/min under oxygen atmosphere, and preserving heat for 10 hours to obtain a layered oxide;
s2, layered oxide and 44.32g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 650 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and sieved to obtain the anode material.
Comparative example 1
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 0.9g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 970 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 23.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 810 ℃ at the speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and sieved to obtain the anode material.
Comparative example 2
The positive electrode material (Na 1.11 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.598kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 25.98g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 790 ℃ at the speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and sieved to obtain the anode material.
Comparative example 3
The positive electrode material (Na 0.89 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.083kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 20.83g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 803 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and sieved to obtain the anode material.
Comparative example 4
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.3g/cm 3 Specific surface area of 35m 2 After mixing at high speed, heating to 970 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layer to be laminatedForm oxide and 23.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 800 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and sieved to obtain the anode material.
Comparative example 5
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 2.2g/cm 3 Specific surface area of 9m 2 After mixing at high speed, heating to 1200 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 23.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 783 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and screened to obtain the anode material.
Comparative example 6
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 7 hours to obtain a layered oxide;
s2, layered oxide and 23.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 793 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and screened to obtain the anode material.
Comparative example 7
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 25 hours to obtain a layered oxide;
s2, layered oxide and 23.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 787 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and screened to obtain the anode material.
Comparative example 8
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 23.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 777 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 20 hours, and the mixture is crushed and screened to obtain the anode material.
Comparative example 9
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 3 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 23.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 817 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation for 20 hours, and the mixture is crushed and screened to obtain the anode material.
Comparative example 10
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 5 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, directly heating the layered oxide to 850 ℃ at a speed of 3 ℃/min under the air atmosphere, carrying out heat preservation treatment for 20 hours, and crushing and screening to obtain the anode material.
Comparative example 11
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After high-speed mixing/g) under an air atmosphere,heating to 1000 ℃ at a speed of 5 ℃/min, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 49.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 738 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation for 20 hours, and the mixture is crushed and sieved to obtain the anode material.
Comparative example 12
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 5 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 23.64g of Na 2 CO 3 And (the purity is 99.68 percent), after being uniformly mixed, the mixture is heated to 783 ℃ at a speed of 3 ℃/min under the air atmosphere, and is subjected to heat preservation treatment for 25 hours, and the mixture is crushed and screened to obtain the anode material.
Comparative example 13
The positive electrode material (Na 1.01 Cu 0.08 Mn 0.32 Ni 0.24 Fe 0.36 O 2 ) The preparation method of (2) comprises the following steps:
s1, 2.364kg Na 2 CO 3 (purity 99.68%) and 4kg of nickel copper iron manganese hydroxide (Cu) 0.08 Mn 0.32 Ni 0.24 Fe 0.36 (OH) 2 Tap density of 1.6g/cm 3 Specific surface area of 30m 2 After mixing at high speed, heating to 1000 ℃ at a speed of 5 ℃/min under the air atmosphere, and carrying out heat preservation treatment for 15 hours to obtain a layered oxide;
s2, layered oxide and 23.64g of Na 2 CO 3 (purity is 99.68%) and then, under the air atmosphere,heating to 831 ℃ at a speed of 3 ℃/min, preserving heat for 7 hours, crushing and screening to obtain the anode material.
Test example 1
The layered oxide of example 1, the positive electrode material of example 4, the positive electrode material of comparative example 8, and the positive electrode material of comparative example 9 were subjected to scanning electron microscopy, and the results are shown in fig. 1, 2, 3, 4, and 5.
From fig. 1 to 5, it can be seen that the morphology of the layered oxide is large and flake, and after sintering at the temperature and parameters satisfying the relation of the present invention, the morphology of the material can be improved, and the morphology is more round.
The parameters of the layered oxides and the positive electrode materials of examples 1 to 6 and comparative examples 1 to 13 were measured, and the results are shown in table 1.
In table 1, TD is the tap density of the layered oxide, and the test method is: weighing 50+/-0.01 g of sample by using a 50mL measuring cylinder, vibrating at 200times/min and 3+/-0.2 mm in amplitude, and vibrating for 3000times;
s is the specific surface area (BET) of the layered oxide, and the test method is as follows: weighing 4.000+/-0.001 g of sample, putting the sample into a bulb star tube, and degassing at 150 ℃ for 60min, wherein the volume ratio of adsorbate is 4:1, a mixture of helium and nitrogen;
beta is the mass ratio of the sodium element in the layered oxide to the sodium source in the step S2, namely the mass ratio of the sodium source in the step S2 to the sodium source in the step S1;
t is the sintering temperature in the step S2;
P 1 is the dullness of the layered oxide; p (P) 2 Is the dullness of the positive electrode material; the method for testing the bluff degree comprises the following steps: the statistical analysis of the granularity and shape of 100 particles which are more than 20000 is carried out by adopting a rice spectrum technology W-3000 granularity and shape instrument, and the blunting degree is aimed at a blunt end model in a wind tunnel experiment and aerodynamic is cited. The front section of the blunt model is a small arc, the rear section is a cylinder, and an arch section is connected between the rear section and the front section. The arch segment is tangential to the front portion. Blunt = tip arc diameter +.post cylinder diameter x 100%. Generally, the diameter of the rear cylinder is fixed, and the diameter of the top circular arc is changed to study the blunt effect.
TABLE 1
As can be seen from Table 1, the preparation method of the positive electrode material can obviously improve the morphology of the material and the dullness of the material.
Test example 2
Positive electrode sheets were prepared using the layered positive electrode materials prepared in examples 1 to 6 and comparative examples 1 to 13, respectively, and the rolled state of each positive electrode sheet was tested, and the results thereof are recorded in table 2.
The testing method comprises the following steps: the positive electrode materials, the conductive agent SP and the binder PVDF prepared in the examples and the comparative examples are respectively prepared according to the mass ratio of 97.3:0.7:2, mixing with N-methyl pyrrolidone serving as a solvent and anhydrous oxalic acid to form positive electrode slurry, coating the positive electrode slurry on the surface of an aluminum foil of a current collector, drying, and rolling until the equipment limit is reached or the aluminum foil is not broken or the average value of the compacted density is kept at 3.25+/-0.1 g/cm 3 。
And (3) battery assembly: the positive electrode materials of examples 1 to 6 and comparative examples 1 to 13 were used as active materials, respectively, and the following active materials were used: SP: the mass ratio of PVDF is 90:5:5, mixing, adding NMP to prepare adhesive solution with viscosity, coating the adhesive solution on aluminum foil, and baking the adhesive solution for 12 hours at 120 ℃ in a vacuum drying oven to obtain the positive plate. The positive plate, the metal sodium plate as the counter electrode, the glass fiber (Waterman) as the diaphragm, 1mol/L NaPF are adopted 6 EC/dmc=1: 1 (Alfa) as an electrolyte, a 2032 button cell was assembled in an Ar protection glove box. Testing the batteries in a voltage range of 2.5-4V, circulating the batteries for 3 weeks at 0.1C, and recording the discharge specific capacity and first effect of the 5 batteries at 0.1C for 3 weeks on average; the results are recorded in table 2.
TABLE 2
As can be seen from table 1, in the preparation method of the positive electrode material according to the present invention, the relational expression of the present invention is satisfied, and the tap density and specific surface area of the nickel-copper-iron-manganese hydroxide, δ, β, tap density and specific surface area of the layered oxide, and sintering time are in a proper range, which is beneficial to improving the fluidity of the prepared positive electrode material, thereby improving the compaction density and cycle performance of the positive electrode sheet.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.

Claims (10)

1. The preparation method of the positive electrode material is characterized by comprising the following steps:
carrying out first sintering on the layered oxide and a sodium source at the temperature of T+/-20 ℃ to obtain the anode material;
wherein t=850-td×100×t/s×β; TD is the value of the tap density of the layered oxide, the unit of tap density is g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the S is the value of the specific surface area of the layered oxide, and the unit of the specific surface area is m 2 /g; t is the value of the time of the first sintering, and the unit of time is h; beta is the mass ratio of Na element in the sodium source and Na element in the layered oxide.
2. The method for producing a positive electrode material according to claim 1, wherein β is 0.0001 to 0.02.
3. The method of producing a positive electrode material according to claim 1, characterized by comprising at least one of the following features (1) to (3);
(1) The layered oxide includes Na δ Cu y Ni z Fe s Mn t (OH) 2 ；0.9≤δ≤1.1，0.08≤y≤0.14，0.18≤z≤0.24，0.3≤s≤0.36，0.32≤t≤0.35，y+z+s+t＝1；
(2) The tap density of the layered oxide is 1-2 g/cm 3 ；
(3) The specific surface area of the layered oxide is 0.3-1 m 2 /g。
4. The method for producing a positive electrode material according to claim 1, wherein the time for the first sintering is 8 to 24 hours.
5. The method for producing a positive electrode material according to claim 1, characterized in that the method for producing a layered oxide comprises the steps of:
and (3) performing second sintering on the sodium source and the nickel-copper-iron-manganese hydroxide to obtain the layered oxide.
6. The method for preparing a positive electrode material according to claim 5, wherein the nickel-copper-iron-manganese hydroxide has a chemical formula of Cu y Ni z Fe s Mn t (OH) 2 ；0.08≤y≤0.14，0.18≤z≤0.24，0.3≤s≤0.36，0.32≤t≤0.35，y+z+s+t＝1。
7. The method for producing a positive electrode material according to claim 5, characterized by comprising at least one of the following features (1) to (3);
(1) The particle size D50 of the nickel-copper-iron-manganese hydroxide is 4-10 mu m;
(2) The tap density of the nickel-copper-iron-manganese hydroxide is more than or equal to 1g/cm 3 ；
(3) By a means ofThe specific surface area of the nickel-copper-iron-manganese hydroxide is 10-30 m 2 /g。
8. The method for producing a positive electrode material according to claim 5, wherein the second sintering comprises: heat preservation is carried out for 8 to 24 hours at 950 to 1200 ℃.
9. A positive electrode material, characterized by being produced by the method for producing a positive electrode material according to any one of claims 1 to 8.
10. A positive electrode sheet comprising the positive electrode material according to claim 9.
CN202311592510.8A 2023-11-27 2023-11-27 Positive electrode material, preparation method thereof and positive electrode plate Pending CN117374212A (en)

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Publication number Priority date Publication date Assignee Title
CN117558912A (en) * 2024-01-11 2024-02-13 广东省中科海钠科技有限责任公司 Positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117558912A (en) * 2024-01-11 2024-02-13 广东省中科海钠科技有限责任公司 Positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment
CN117558912B (en) * 2024-01-11 2024-04-23 广东省中科海钠科技有限责任公司 Positive electrode material, preparation method thereof, positive electrode plate, sodium ion battery and electric equipment

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