CN113851654B - Cathode material for relieving oxygen release, and preparation method and application thereof - Google Patents

Cathode material for relieving oxygen release, and preparation method and application thereof Download PDF

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CN113851654B
CN113851654B CN202111105668.9A CN202111105668A CN113851654B CN 113851654 B CN113851654 B CN 113851654B CN 202111105668 A CN202111105668 A CN 202111105668A CN 113851654 B CN113851654 B CN 113851654B
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positive electrode
copper sulfide
equal
battery
preparation
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CN113851654A (en
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郑晓醒
江卫军
李子郯
陈思贤
杨红新
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Svolt Energy Technology Co Ltd
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Abstract

The invention provides a positive electrode material for relieving oxygen release, a preparation method and application thereof. The copper sulfide has reducibility, when the battery is out of control due to heat, the anode material is decomposed to generate an oxygen release condition, the copper sulfide coated on the surface of the anode material can reduce and fix oxygen, the combustible electrolyte is prevented from being ignited by the released oxygen under the condition of heat accumulation, and the risk of the battery out of control due to heat is reduced. And the copper sulfide can be used as a lithium battery anode material, has excellent electronic conductivity and reversible ionic conduction performance, and has high specific capacity. The positive electrode material can be used as a positive electrode material coating layer to effectively reduce the internal resistance of the battery, improve the multiplying power and the cycle performance, simultaneously improve the capacity exertion of positive electrode active substances and effectively improve the energy density of the battery.

Description

Cathode material for relieving oxygen release, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of anode materials, and relates to an anode material for relieving oxygen release, a preparation method and application thereof.
Background
The high energy density lithium ion battery is the key to promote the next generation of sustainable energy technology. The oxygen-containing anode is a main component of a high-voltage and high-energy-density lithium ion battery. Since graphite is used as the negative electrode in most commercial lithium ion batteries, the electrochemical performance (e.g., energy density and operating voltage) of the battery is determined by the choice of the positive electrode material. The main technical route at present is to use a high-nickel and high-voltage cathode material, and the research at present shows that the ultrahigh specific capacity is not only derived from the oxidation reduction of the conventional transition metal cation, but also relates to the reversible participation of anionic oxygen in electrochemical reaction.
The redox reaction of the anion involves a reversible moiety (O) that occurs predominantly in the bulk phase 2- →O 2 n- ) And irreversible oxygen evolution (O) mainly occurring at the surface 2- →O 2 ). The latter seriously deteriorates the electrochemical performance of the lithium-rich material, and the deterioration process is mainly reflected in two aspects of the material structure and the decomposition of the external electrolyte. Specifically, oxygen on the surface of the lithium-rich material escapes from lattice positions to cause instability of the crystal framework, and the transition metal migrates from the transition metal layer to the adjacent lithium layer to balance stability, so that local phase transition from a layered phase to a spinel-like phase is generated and gradually expands to the inside of the bulk phase, and the phase transition causes a series of adverse effects such as capacity attenuation, voltage drop and kinetic resistance due to occupation of lithium transport channels in the spinel-like phase. On the other hand, the escaped oxygen has high reactivity, and will attack the electrolyte at the electrode/electrolyte interface, resulting in unstable SEI and corresponding proton generation, wherein the proton will continue to etch the material and accelerate the progress of these adverse reactions.
Therefore, the high gram capacity of the positive electrode material is improved, and the thermal stability is reduced. The anode material is decomposed at high temperature and high pressure, a large amount of oxygen is released to cause severe degradation of the anode performance, and a large amount of heat and energy are rapidly released to endanger the safety of the battery, and thermal runaway, namely ignition of the battery, is triggered. Thermal runaway events occur from notebook computers, mobile phones to electronic cigarettes, earphones, electric vehicles and even airplanes, and serious damage is caused to consumers. This further underscores the important role of inhibiting oxygen evolution from the positive electrode material in the safety of lithium ion batteries.
CN109037684A discloses an internal oxygen self-absorption safety lithium battery, which comprises a positive plate and a negative plate; the positive plate is prepared from the following raw materials in parts by weight: 90 to 97 parts of positive active material, 0.5 to 4 parts of positive conductive agent, 0.5 to 3 parts of positive binder and 15 to 70 parts of positive solvent; the positive plate also comprises an oxygen absorption additive, and the addition amount of the oxygen absorption additive is 0.01-10% of the total amount of the positive active material, the positive conductive agent and the positive binder.
CN110071278A discloses a high-nickel ternary positive electrode material containing an active oxygen remover, comprising an active oxygen remover and a high-nickel ternary material, wherein the active oxygen remover is coated on the surface of the high-nickel ternary positive electrode material, the invention also provides a preparation method of the high-nickel ternary positive electrode material coated with the active oxygen remover, the high-nickel ternary positive electrode material and the active oxygen remover are dissolved in absolute ethyl alcohol according to a certain mass ratio for ultrasonic dispersion, and a sample is dried in vacuum at 100 ℃ for 12-24 hours after filtration to obtain the high-nickel ternary positive electrode material.
CN111640934A discloses a method for high-temperature solid-phase sintering of a lithium ion cathode material, comprising the following steps: s1, mixing materials: weighing a positive electrode material precursor, a lithium source compound and an oxygen release oxide according to a certain proportion, and uniformly mixing to obtain a mixed material; s2, grinding: grinding the mixed material in the step S1 to obtain a grinding material; s3, drying: drying the grinding material in the step S2 to obtain a dried material; s4, sintering: performing high-temperature solid-phase sintering on the dried material in the step S3 to obtain a lithium ion anode material; oxygen-releasing oxides using A n O m Wherein A is one or more of Mn, co and Ni.
However, in the current coating scheme, the coating material still cannot achieve an ideal coating effect, so that the impedance of the positive plate is increased, and the cycle performance of the battery is reduced, so that the comprehensive performance of the coating material needs to be considered.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the positive electrode material for relieving oxygen release, the preparation method and the application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a positive electrode material for alleviating oxygen release, which comprises positive electrode particles and a copper sulfide layer coated on the surfaces of the positive electrode particles.
The copper sulfide has reducibility, when the battery is out of control due to heat, the anode material is decomposed to generate an oxygen release condition, the copper sulfide coated on the surface of the anode material can reduce and fix oxygen, the combustible electrolyte is prevented from being ignited by the released oxygen under the condition of heat accumulation, and the risk of the battery out of control due to heat is reduced. And the copper sulfide can be used as a lithium battery anode material, has excellent electronic conductivity and reversible ionic conduction performance, and has high specific capacity. The anode material can effectively reduce the internal resistance of the battery, improve the multiplying power and the cycle performance, simultaneously improve the capacity exertion of the anode active matter, and effectively improve the energy density of the battery when being used as an anode material coating layer.
In a preferred embodiment of the present invention, the copper sulfide used in the copper sulfide layer is Cu m S, wherein 1. Ltoreq. M.ltoreq.2, may be, for example, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.0, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and cuprous sulfide is more preferable.
Preferably, the mass fraction of copper sulfide is 0.05 to 2wt%, for example, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, or 2.0wt%, based on 100% of the total mass fraction of copper sulfide and positive electrode particles, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
The invention carries out special requirements and specific limitations on the coating amount of the copper sulfide, when the coating amount of the copper sulfide is lower than 0.05w%, the thickness of a copper sulfide layer is thin, the coating uniformity is poor, the coating layer is in punctiform or discontinuous coating, the effect of inhibiting oxygen release of the cathode material is poor, the electronic conductivity of the cathode material is not obviously improved, and the electrochemical performance of the cathode material is not obviously improved; when the coating amount of the copper sulfide is more than 2wt%, the thickness of the copper sulfide layer is thick, which may result in an increase in internal resistance of the battery, resulting in a decrease in cycle and rate performance of the battery.
As a preferable technical scheme of the invention, the positive electrode particles comprise Li 1+x Ni y Co z Mn t M s O 2-δ 、LiM a Mn 2-a O 4 、LiFe 1-b M b PO 4 、Li 2 Fe 1-n M n SiO 4 Or LiFe 1-d M d SO 4 Any one of or a combination of at least two of F.
Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, y + z + t + s =1; 0. Ltoreq. Delta. Ltoreq.0.2, 0. Ltoreq. A.ltoreq.0.5, 0. Ltoreq. B.ltoreq.1, 0. Ltoreq. N.ltoreq.1, 0. Ltoreq. D.ltoreq.1, for example x can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, y can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, t can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, s can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, δ may be 0.01, 0.02, 0.04, 0.06, 0.08, 0.1, 0.12, 0.14, 0.16, 0.18 or 0.2, a may be 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45 or 0.5, b may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, n may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, d may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9, but not limited to the recited values, and the same applies to other values not limited to the recited ranges.
It should be noted that, the various cathode materials provided by the present invention are only described as examples, and do not form specific limitations on the cathode materials adopted by the present invention, and the cathode materials disclosed in the prior art or not disclosed in the new technology can be used in the present invention, and can also achieve the technical solutions that can be achieved by the present invention.
M is selected from any one of Li, na, K, mg, ca, sr, ba, al, ga, in, si, ge, sn, pb, sc, V, cr, mn, fe, co, ni, cu, zn, Y, zr, nb, mo, ru, rh, pd, ag, cd, la, ce, pr, nd, sm, eu, gd, er, tm, yb, lu, W, pt or Au.
In a second aspect, the present invention provides a method for preparing the positive electrode material of the first aspect, wherein the positive electrode material is prepared by dry coating.
The main point of the present invention is to suppress oxygen release from the positive electrode active particles by coating the copper sulfide layer. The preparation method and the coating method of the cathode material are not particularly required or limited, and exemplarily, the dry coating or the atomic layer deposition coating and the like defined by the invention can be used for preparing the cathode material defined by the invention, and the finally prepared cathode material can also achieve the same effect of inhibiting oxygen release.
As a preferred technical scheme of the present invention, the preparation method specifically comprises the following steps:
and (3) mixing the copper sulfide with the positive electrode particles, and then carrying out annealing treatment, wherein the copper sulfide coats the surfaces of the positive electrode particles to form a copper sulfide layer.
In a preferred embodiment of the present invention, the mass fraction of the copper sulfide is 0.05 to 2wt%, for example, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, or 2.0wt%, based on 100% of the total mass fraction of the copper sulfide and the positive electrode particles, but is not limited to the recited values, and other values not recited in the range are also applicable.
In a preferred embodiment of the present invention, the mixing time is 5 to 30min, for example, 5min, 10min, 15min, 20min, 25min or 30min, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
Preferably, the mixing is with mechanical agitation.
Preferably, the mechanical agitation is at a speed of 500 to 4000rpm, for example 500rpm, 1000rpm, 1500rpm, 2000rpm, 2500rpm, 3000rpm, 3500rpm or 4000rpm, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
In a preferred embodiment of the present invention, the annealing temperature is 200 to 600 ℃, and may be, for example, 200 ℃, 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
It should be noted that the annealing temperature used in the present invention is not too high, otherwise the strong reducibility of the copper sulfide would reduce the positive electrode particles, thereby affecting the electrochemical performance of the positive electrode material.
Preferably, the annealing time is 3 to 8 hours, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the treatment atmosphere of the annealing is an inert atmosphere.
As a preferred technical solution of the present invention, after the annealing is completed, the prepared positive electrode material is sieved.
Preferably, the screening process uses a screen mesh number of 300-400, such as 300 mesh, 310 mesh, 320 mesh, 330 mesh, 340 mesh, 350 mesh, 360 mesh, 370 mesh, 380 mesh, 390 mesh or 400 mesh, but not limited to the listed values, and other values not listed in the range of values are also applicable.
In a third aspect, the invention provides a battery, which comprises a positive plate, a diaphragm and a negative plate which are sequentially stacked, wherein the positive plate comprises a current collector and positive active slurry coated on the surface of the current collector, and the positive active slurry comprises the positive material in the first aspect.
Compared with the prior art, the invention has the beneficial effects that:
the copper sulfide has reducibility, when the battery is out of control due to heat, the anode material is decomposed to generate an oxygen release condition, the copper sulfide coated on the surface of the anode material can reduce and fix oxygen, the combustible electrolyte is prevented from being ignited by the released oxygen under the condition of heat accumulation, and the risk of the battery out of control due to heat is reduced. The copper sulfide can be used as a lithium battery anode material, has excellent electronic conductivity and reversible ion conduction performance, and has high specific capacity. The positive electrode material can be used as a positive electrode material coating layer to effectively reduce the internal resistance of the battery, improve the multiplying power and the cycle performance, simultaneously improve the capacity exertion of positive electrode active substances and effectively improve the energy density of the battery.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a positive electrode material, which comprises positive electrode particles and a CuS layer coated on the surfaces of the positive electrode particles, wherein the positive electrode particles have a chemical general formula LiNi 0.83 Co 0.01 Mn 0.06 O 2 The coating amount of the CuS layer was 0.1wt%.
The embodiment also provides a preparation method of the cathode material, and the preparation method specifically comprises the following steps:
(1) CuS and LiNi 0.8 Co 0.1 Mn 0.1 O 2 Mechanically stirring the positive electrode particles after mixing for 5min, wherein the rotation speed of the mechanical stirring is 4000rpm, and the mass fraction of CuS is 0.1wt% based on 100% of the total mass fraction of CuS and the positive electrode particles;
(3) Placing the mixed powder in a nitrogen atmosphere for annealing treatment, wherein the annealing temperature is 200 ℃, and the annealing time is 8 hours;
(4) After the annealing is finished, the prepared anode material passes through a 300-mesh screen.
Example 2
The embodiment provides a positive electrode material, which comprises positive electrode particles and a coatingCu on the surface of the positive electrode particle 1.2 S layer, wherein the chemical formula of the anode particles is LiNi 0.83 Co 0.01 Mn 0.06 O 2 The coating amount of (2) was 0.5wt%.
The embodiment also provides a preparation method of the cathode material, and the preparation method specifically comprises the following steps:
(2)Cu 1.2 s and LiNi 0.83 Co 0.01 Mn 0.06 O 2 Mixing the positive electrode particles, and mechanically stirring at 3000rpm for 10min 1.2 The total mass fraction of S and the positive electrode particles is 100 percent, wherein Cu 1.2 The mass fraction of S is 0.5wt%;
(3) Placing the mixed powder in an argon atmosphere for annealing treatment, wherein the annealing temperature is 250 ℃, and the annealing time is 6 hours;
(4) After the annealing is finished, the prepared cathode material is screened by a 350-mesh screen.
Example 3
The embodiment provides a positive electrode material, which comprises positive electrode particles and Cu coated on the surfaces of the positive electrode particles 1.5 S layer, wherein the chemical general formula of the positive electrode particles is LiNi 0.83 Co 0.01 Mn 0.06 O 2 The coating amount of the layer was 1wt%.
The embodiment also provides a preparation method of the cathode material, and the preparation method specifically comprises the following steps:
(2)Cu 1.5 s and LiNi 0.83 Co 0.01 Mn 0.06 O 2 Mixing the positive electrode particles, and mechanically stirring at 2000rpm for 15min 1.5 The total mass fraction of the S powder and the positive electrode particles is 100 percent, wherein Cu 1.5 The mass fraction of the S powder is 1wt%;
(3) Placing the mixed powder in an argon atmosphere for annealing treatment, wherein the annealing temperature is 280 ℃, and the annealing time is 8 hours;
(4) After the annealing is finished, the prepared cathode material is screened by a 400-mesh screen.
Example 4
The embodiment provides a positive electrode material, which comprises positive electrode particles and Cu coated on the surfaces of the positive electrode particles 1.8 S layer, wherein the chemical general formula of the positive electrode particles is LiNi 0.83 Co 0.01 Mn 0.06 O 2 ，Cu 1.8 The coating amount of the S layer was 3wt%.
The embodiment also provides a preparation method of the cathode material, and the preparation method specifically comprises the following steps:
(1)Cu 1.8 s and LiNi 0.83 Co 0.01 Mn 0.06 O 2 Mixing the positive electrode particles, and mechanically stirring at 1000rpm for 20min 1.8 The total mass fraction of S and the positive electrode particles is 100 percent, wherein Cu 1.8 The mass fraction of S is 3wt%;
(3) Placing the mixed powder in a helium atmosphere for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 5 hours;
(4) After the annealing is finished, the prepared cathode material is screened by a 320-mesh screen.
Example 5
The embodiment provides a positive electrode material, which comprises positive electrode particles and Cu coated on the surfaces of the positive electrode particles 2 S layer, wherein the chemical general formula of the positive electrode particles is LiNi 0.83 Co 0.01 Mn 0.06 O 2 ，Cu 2 The coating amount of the S layer was 5wt%.
The embodiment also provides a preparation method of the cathode material, and the preparation method specifically comprises the following steps:
(1)Cu 2 s and LiNi 0.83 Co 0.01 Mn 0.06 O 2 After the positive electrode particles are mixed, the mixture is mechanically stirred for 30min, the rotating speed of the mechanical stirring is 500rpm, and Cu is used 2 The total mass fraction of S and the positive electrode particles is 100 percent, wherein Cu 2 The mass fraction of S is5wt％；
(3) Placing the mixed powder in an argon atmosphere for annealing treatment, wherein the annealing temperature is 600 ℃, and the annealing time is 3 hours;
(4) After the annealing is finished, the prepared cathode material is screened by a 400-mesh screen.
Example 6
This example differs from example 5 in that in step (1) of the production method, cu is added 2 The mass fraction of S was adjusted to 0.05wt%, and other process parameters and operation steps were exactly the same as in example 1.
Example 7
This example differs from example 5 in that in step (1) of the production method, cu is added 2 The mass fraction of S was adjusted to 8wt%, and other process parameters and operation steps were exactly the same as in example 1.
Example 8
The embodiment provides a positive electrode material, which comprises positive electrode particles and Cu coated on the surfaces of the positive electrode particles 2 S layer, wherein the chemical general formula of the positive electrode particles is LiNi 0.75 Mn 0.25 O 2 The coating amount of the layer was 1wt%.
The embodiment also provides a preparation method of the cathode material, and the preparation method specifically comprises the following steps:
(2)Cu 2 s and LiNi 0.75 Mn 0.25 O 2 Mixing the positive electrode particles, and mechanically stirring at 2000rpm for 15min 2 The total mass fraction of the S powder and the positive electrode particles is 100 percent, wherein Cu 2 The mass fraction of the S powder is 1wt%;
(3) Placing the mixed powder in an air atmosphere for annealing treatment, wherein the annealing temperature is 400 ℃, and the annealing time is 8 hours;
(4) After the annealing is finished, the prepared cathode material is screened by a 400-mesh screen.
Comparative example 1
This comparative example provides a positive electrode material that is identical to the positive electrode material provided in example 5, except that the positive electrode material provided in this comparative example is not coated with Cu 2 And (5) an S layer.
Comparative example 2
This comparative example provides a positive electrode material that is identical to the positive electrode material provided in example 8, except that the positive electrode material provided in this comparative example is not coated with Cu 2 And (5) an S layer.
Oxygen release test: the oxygen release conditions of the positive electrode materials provided in examples 1 to 10 and comparative example 1 were tested by TG-MS under the following test conditions: the temperature is gradually increased from room temperature to 300 ℃ at the temperature increase rate of 10 ℃/min, the gas atmosphere of the test environment is argon, the mass fraction decrease rate of the anode material is measured, the temperature of the anode material when oxygen release starts is detected, and the test results are shown in table 1.
Electrochemical performance test, the test process comprises:
(1) Preparing a positive plate: 1.094g of PVDF-NMP solution with the solid content of 6.25wt%, 0.8g of NMP solution, 0.068g of conductive carbon and 1.574g of the positive electrode material prepared in the comparative example and the embodiment are taken, homogenized, coated (the gap between scrapers is 22 mu m), dried and rolled to obtain the positive electrode sheet.
(2) And (3) buckling and assembling: the negative electrode is made of lithium metal, the diaphragm is made of PE, the electrolyte is LiPF6 (the concentration of the LiPF6 in the electrolyte is 1M), the LiPF6 is dissolved in a mixed solution of Ethylene Carbonate (EC)/diethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) in a volume ratio of 1.
TG-MS test: the TG-MS test was performed using a fully charged positive plate to obtain the initial oxygen release temperature of the positive electrode material, as shown in table 1.
TABLE 1
Figure BDA0003272212050000111
Figure BDA0003272212050000121
As can be seen from the data of table 1, the oxygen release temperatures in examples 1 to 8 are all higher than those of the comparative example, and it can be seen that the temperature at the time of oxygen release is increased by coating the copper sulfide, thereby effectively suppressing oxygen release from the positive electrode material.
As can be seen by comparing the test data of example 5, example 6 and example 7, cu 2 Too high or too low S coating affects Cu 2 S thickness, thereby affecting the effect of suppressing oxygen evolution and the electrochemical properties of the cathode material.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (14)

1. The positive electrode material is characterized by comprising positive electrode particles and a copper sulfide layer coated on the surfaces of the positive electrode particles;
the copper sulfide layer adopts copper sulfide which is cuprous sulfide.
2. The positive electrode material for alleviating oxygen release according to claim 1, wherein the mass fraction of the copper sulfide is 0.05 to 2wt% based on 100% of the total mass fraction of the copper sulfide and the positive electrode particles.
3. The positive electrode material as claimed in claim 1, wherein the positive electrode particles comprise Li 1+ x Ni y Co z Mn t M s O 2-δ 、LiM a Mn 2-a O 4 、LiFe 1-b M b PO 4 、Li 2 Fe 1-n M n SiO 4 Or LiFe 1-d M d SO 4 Any one or a combination of at least two of F;
wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, y + z + t + s =1;
0≤δ≤0.2，0≤a≤0.5，0≤b≤1，0≤n≤1，0≤d≤1；
m is selected from any one of Li, na, K, mg, ca, sr, ba, al, ga, in, si, ge, sn, pb, sc, V, cr, mn, fe, co, ni, cu, zn, Y, zr, nb, mo, ru, rh, pd, ag, cd, la, ce, pr, nd, sm, eu, gd, er, tm, yb, lu, W, pt or Au.
4. The preparation method of the cathode material according to claim 1, wherein the cathode material is prepared by dry coating.
5. The preparation method according to claim 4, wherein the preparation method specifically comprises the following steps:
and (4) mixing the copper sulfide with the positive electrode particles, and then carrying out annealing treatment, wherein the copper sulfide coats the surfaces of the positive electrode particles to form a copper sulfide layer.
6. The production method according to claim 5, wherein the mass fraction of the copper sulfide is 0.05 to 2wt% based on 100% of the total mass fraction of the copper sulfide and the positive electrode particles.
7. The method of claim 5, wherein the mixing is carried out for 5 to 30min.
8. The method of claim 5, wherein the mixing is by mechanical agitation.
9. The method according to claim 8, wherein the rotation speed of the mechanical stirring is 500 to 4000rpm.
10. The method according to claim 5, wherein the annealing temperature is 200 to 600 ℃.
11. The production method according to claim 5, wherein the annealing time is 3 to 8 hours.
12. The method of claim 5, wherein the annealing treatment atmosphere is an inert atmosphere.
13. The preparation method according to claim 5, wherein after the annealing is finished, the prepared positive electrode material is sieved;
the mesh number of the screen adopted in the screening process is 300 to 400 meshes.
14. A battery, characterized in that, the battery comprises a positive plate, a diaphragm and a negative plate which are sequentially laminated, the positive plate comprises a current collector and positive active slurry coated on the surface of the current collector, and the positive active slurry comprises the positive material of any one of claims 1-3.
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