CN109888200A - Battery cathode coating, battery cathode sheet and its manufacturing method, lithium ion battery - Google Patents
Battery cathode coating, battery cathode sheet and its manufacturing method, lithium ion battery Download PDFInfo
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- CN109888200A CN109888200A CN201811646579.3A CN201811646579A CN109888200A CN 109888200 A CN109888200 A CN 109888200A CN 201811646579 A CN201811646579 A CN 201811646579A CN 109888200 A CN109888200 A CN 109888200A
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Abstract
The present invention is suitable for field of lithium ion battery, disclose battery cathode coating, battery cathode sheet, the manufacturing method of battery cathode sheet, lithium ion battery, wherein, the component of battery cathode coating includes negative electrode active material, cathode conductive agent, suspending agent and negative electrode binder, and negative electrode active material includes synthetic graphite particles and the hard carbon material layer that is coated on outside synthetic graphite particles.The present invention is due to using the synthetic graphite particles for being coated with hard carbon material as negative electrode active material; therefore; forming protective layer outside synthetic graphite particles using hard carbon material layer prevents the solvent molecule of electrolyte to be embedded into cathode graphite-structure layer; and the conductive characteristic that can be good of hard carbon material, thus be conducive to further promote the cycle performance of lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a battery negative electrode coating, a battery negative electrode sheet, a manufacturing method of the battery negative electrode sheet and a lithium ion battery.
Background
The negative plate of the lithium ion battery generally comprises a negative metal substrate and a negative coating coated outside the negative metal substrate, wherein the components of the negative coating generally comprise a negative active material, a negative conductive agent, a suspending agent and a negative binder.
In the existing lithium ion battery, graphite is generally used as a negative active material. In the specific application of the lithium ion battery, solvent molecules of the electrolyte are easy to be inserted into a graphite crystal structure layer along with lithium ions (namely, an 'electrolyte solvent molecule co-insertion' reaction occurs), so that a negative graphite layered structure is damaged, and then negative graphite powder falls off, thereby shortening the cycle life of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a battery cathode coating, which aims to solve the technical problem that the cycle life of a lithium ion battery is shortened due to the co-intercalation of electrolyte solvent molecules in the conventional lithium ion battery.
In order to achieve the purpose, the invention provides the following scheme: the battery negative electrode coating comprises negative electrode active materials, a negative electrode conductive agent, a suspending agent and a negative electrode binder, wherein the negative electrode active materials comprise artificial graphite particles and a hard carbon material layer coated outside the artificial graphite particles.
Optionally, the battery negative electrode coating comprises the following components in parts by weight: 94.0-97.0 percent of negative electrode active material, 0.2-2.2 percent of negative electrode conductive agent, 1.2-2.0 percent of suspending agent and 1.4-2.4 percent of negative electrode binder.
Optionally, the battery negative electrode coating comprises the following components in parts by weight: 95.0% of negative electrode active material, 1.5% of negative electrode conductive agent, 1.3% of suspending agent and 2.2% of negative electrode binder; or,
the battery negative electrode coating comprises the following components in parts by weight: 94.0% of negative electrode active material, 1.6% of negative electrode conductive agent, 2.0% of suspending agent and 2.4% of negative electrode binder; or,
the battery negative electrode coating comprises the following components in parts by weight: 97.0% of negative electrode active material, 0.3% of negative electrode conductive agent, 1.2% of suspending agent and 1.5% of negative electrode binder.
Optionally, the hard carbon material layer is made of carbon black; and/or the presence of a gas in the atmosphere,
the negative electrode conductive agent comprises at least one of conductive carbon black, conductive graphite and carbon nano tubes; and/or the presence of a gas in the atmosphere,
the negative electrode binder comprises at least one of sodium carboxymethylcellulose, styrene butadiene rubber, polyacrylic acid and sodium alginate; and/or the presence of a gas in the atmosphere,
the suspending agent is sodium carboxymethyl cellulose.
The invention also provides a battery negative plate, which comprises a negative metal substrate, a negative lug electrically connected with the negative metal substrate and a negative coating coated outside the negative metal substrate.
The third object of the present invention is to provide a method for manufacturing the battery negative electrode sheet, which comprises the following steps:
adding the suspending agent dry powder into deionized water, and mixing to obtain suspending agent glue solution;
mixing a negative electrode active substance, a negative electrode conductive agent and 50-70% of the suspending agent glue solution to prepare a negative electrode semi-finished product slurry;
adding a negative electrode binder and the rest of the suspending agent glue solution into the negative electrode semi-finished product slurry, mixing, adding deionized water, and continuously mixing to prepare a negative electrode slurry;
coating the negative electrode slurry on a negative electrode metal substrate to obtain a negative electrode coating intermediate product;
drying and curing the cathode coating intermediate product to dry and cure the cathode slurry into a battery cathode coating, thereby preparing a cathode cured intermediate product;
sequentially rolling and cutting the anode cured intermediate product to obtain a semi-finished cathode plate;
and welding negative electrode lugs on the semi-finished product of the negative electrode plate to obtain the battery negative electrode plate.
A fourth object of the present invention is to provide a lithium ion battery, which includes a battery case, a battery positive plate, a first diaphragm, a second diaphragm, an electrolyte and the battery negative plate, wherein the battery positive plate, the battery negative plate, the first diaphragm, the second diaphragm and the electrolyte are all disposed in the battery case, the battery positive plate, the battery negative plate, the first diaphragm and the second diaphragm are all immersed in the electrolyte, the battery negative plate is located between the battery positive plate and the battery case, the first diaphragm is disposed between the battery positive plate and the battery negative plate, and the second diaphragm is disposed between the battery case and the battery negative plate.
Optionally, the battery positive plate comprises a positive metal substrate, a positive lug in conductive connection with the positive metal substrate, and a battery positive coating coated outside the positive metal substrate, the components of the battery positive coating comprise a positive active material, a positive binder and a positive conductive agent, and the median particle diameter D of the positive active material50Is 7mm +/-3 microns.
Optionally, the positive active material comprises a ternary material LiNixMnyCozO2Particles and LiNi coated on the ternary materialxMnyCozO2A coating layer outside the particles, wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z is 1.0;
the coating layer comprises MgO and Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of; or,
the components of the battery anode coating comprise an anode active substance, an anode binder and an anode conductive agent, wherein the anode active substance comprises a ternary material LiNixMnyCozO2Particles and LiNi doped in the ternary materialxMnyCozO2Doping elements in particles and LiNi coated on the ternary materialxMnyCozO2A coating layer outside the particles, wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z is 1.0;
the doping element comprises at least one of Al and F;
the coating layer comprises MgO and Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of (1).
Optionally, the concentration of lithium salt in the electrolyte is 1.1-1.3 mol/L; and/or the presence of a gas in the atmosphere,
the electrolyte contains at least one of LiFSI and TMSP.
The invention has the beneficial effects that:
because the artificial graphite particles coated with the hard carbon material are used as the negative active material, the hard carbon material layer can form a protective layer outside the artificial graphite particles to prevent solvent molecules of electrolyte from being embedded into a negative graphite structure layer, and the hard carbon material has the characteristic of good conductivity, so that the internal resistance of the battery is favorably reduced, the cycle performance of the lithium ion battery is further improved, and the cycle life of the lithium ion battery is effectively prolonged finally.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a negative electrode sheet of a battery provided by an embodiment of the invention;
fig. 2 is a schematic structural diagram of a positive plate of a battery provided by an embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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 invention.
It should be noted that all the directional indicators (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
It will also be understood that when an element is referred to as being "secured to" or "disposed on" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
In addition, the descriptions related to "first", "second", etc. in the present invention are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The first embodiment is as follows:
as shown in fig. 1-2, a battery negative electrode coating 22 according to an embodiment of the present invention includes a negative electrode active material, a negative electrode conductive agent, a suspending agent, and a negative electrode binder, where the negative electrode active material includes artificial graphite particles and a hard carbon material layer coated on the artificial graphite particles. The artificial graphite is made of amorphous carbon material N2Graphitizing at high temperature (> 2500 ℃) in the atmosphere. The hard carbon material is pyrolytic carbon formed after thermal decomposition of a high molecular polymer, is difficult to graphitize, has good conductivity, helps to reduce the internal resistance of the lithium ion battery and improve the cycle performance, and can prevent solvent molecules of electrolyte from being embedded into a negative electrode graphite structure layer. In this embodiment, the artificial graphite particles coated with the hard carbon material are used as the negative electrode active material, so that the hard carbon material layer can form a protective layer outside the artificial graphite particles to prevent the solvent of the electrolyteThe molecules are embedded into the negative graphite structure layer, and the hard carbon material has the characteristic of good conductivity, so that the internal resistance of the battery is favorably reduced, the cycle performance of the lithium ion battery is further improved, and the cycle life of the lithium ion battery is effectively prolonged finally.
Preferably, the battery negative electrode coating 22 comprises the following components in parts by weight: 94.0-97.0 percent of negative electrode active material, 0.2-2.2 percent of negative electrode conductive agent, 1.2-2.0 percent of suspending agent and 1.4-2.4 percent of negative electrode binder. Here, by optimally designing the component content of the battery negative electrode coating 22, the capacity of the battery negative electrode sheet 2 and the adhesive force of the battery negative electrode coating 22 on the negative electrode metal substrate 21 are improved, the resistance of the battery negative electrode sheet 2 is reduced, and further the capacity, the cycle performance and the safety performance of the lithium ion battery are further improved. In addition, the setting of the suspending agent can ensure that the cathode conductive agent and the cathode active substance are well dispersed and in a suspended state in the prepared cathode slurry, ensure the stability of the subsequent processing process (coating process) of the cathode slurry, avoid the agglomeration of the cathode conductive agent and avoid the sedimentation of the cathode active substance.
More preferably, the battery negative electrode coating 22 comprises the following components in parts by weight: 95.0% of negative electrode active material, 1.5% of negative electrode conductive agent, 1.3% of suspending agent and 2.2% of negative electrode binder; or, the battery negative electrode coating 22 comprises the following components in parts by weight: 94.0% of negative electrode active material, 1.6% of negative electrode conductive agent, 2.0% of suspending agent and 2.4% of negative electrode binder; or, the battery negative electrode coating 22 comprises the following components in parts by weight: 97.0% of negative electrode active material, 0.3% of negative electrode conductive agent, 1.2% of suspending agent and 1.5% of negative electrode binder. Test tests show that the battery negative electrode coating 22 adopts the components in parts by weight, and the effects of improving the capacity of the battery negative electrode sheet 2, improving the adhesive force of the battery negative electrode coating 22 on the negative electrode metal substrate 21 and reducing the resistance of the battery negative electrode sheet 2 are obvious.
Preferably, the hard carbon material layer is made of carbon black, is difficult to graphitize, has good conductivity, and can prevent solvent molecules of the electrolyte from being embedded into the negative electrode graphite structure layer.
More preferably, the hard carbon material layer is made of acetylene black.
Preferably, the negative electrode conductive agent includes at least one of conductive carbon black, conductive graphite, and carbon nanotubes. Here, the material of the negative electrode conductive agent is optimally designed, which is beneficial to reducing the internal resistance of the battery.
More preferably, the negative electrode conductive agent includes at least one of conductive carbon black Super P, 350G, SP-Li, conductive graphite KS-6, conductive graphite SFG-6, Ketjen black ECP-600JD, and carbon nanotube CNT.
Preferably, the negative electrode binder includes at least one of sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), and sodium alginate. Here, the material of the negative electrode binder is optimally designed, which is beneficial to ensuring that the battery negative electrode coating 22 and the negative electrode metal substrate 21 have good adhesion performance. Here, the negative electrode binder is preferably polyacrylic acid. Polyacrylic acid has a long-chain structure similar to SBR, so the binding property of the polyacrylic acid is equivalent to that of SBR; at the same time, it possesses a carboxyl structure, possibly with Li+Formation of lithium carboxylate groups, contributing to the enhancement of Li+The conductivity of the battery is improved, so that the resistance of the pole piece and the internal resistance of the battery are smaller, and the cycle performance of the battery is improved.
Preferably, the suspending agent is sodium carboxymethylcellulose (CMC). Here, the suspending agent is sodium carboxymethylcellulose, which not only can make the negative electrode conductive agent and the negative electrode active material in a suspended state in the prepared negative electrode slurry, but also can improve the adhesion between the components of the battery negative electrode coating 22 and the adhesion between the battery negative electrode coating 22 and the negative electrode metal substrate 21 after the battery negative electrode sheet 2 is dried by utilizing the binding capacity of the sodium carboxymethylcellulose and the synergistic effect of the negative electrode binder.
Further, the embodiment also provides a battery negative electrode sheet 2, which comprises a negative electrode metal substrate 21, a negative electrode tab 23 electrically connected with the negative electrode metal substrate 21, and a negative electrode coating coated outside the negative electrode metal substrate, wherein the negative electrode coating adopts the battery negative electrode coating 23. The negative electrode sheet 2 of the battery provided by the embodiment adopts the negative electrode metal substrate 21, so that the stability and the cycle life of the negative electrode sheet 2 of the battery are improved.
Preferably, the thickness of the negative electrode metal substrate 21 is 8 μm + -2 μm, and the thickness of the battery negative electrode sheet 2 is 147 μm + -5 μm. Thus, the optimum performance of the negative electrode active material is favorably exerted on the premise of ensuring that the size of the battery negative electrode sheet 2 is small. Of course, the thickness of the negative electrode metal substrate 21 and the thickness of the battery negative electrode tab 2 are not limited thereto in specific applications.
Preferably, the negative electrode metal substrate 21 is a copper foil, which can meet the requirement of the conductivity of the battery negative electrode sheet 2, and has light weight and low cost. Of course, the material of the negative electrode metal substrate 21 is not limited to this in specific applications.
Further, the present embodiment also provides a method for manufacturing the battery negative electrode sheet 2, which includes the following steps:
adding the suspending agent dry powder into deionized water, and mixing to obtain suspending agent glue solution;
mixing a negative electrode active substance, a negative electrode conductive agent and 50-70% of the suspending agent glue solution to prepare a negative electrode semi-finished product slurry;
adding a negative electrode binder and the rest of the suspending agent glue solution into the negative electrode semi-finished product slurry, mixing, adding deionized water, and continuously mixing to prepare a negative electrode slurry;
coating the cathode slurry on a cathode metal substrate 21 to prepare a cathode coating intermediate product;
drying and curing the cathode coating intermediate product to dry and cure the cathode slurry into a battery cathode coating 22 to obtain a cathode cured intermediate product;
sequentially rolling and cutting the anode cured intermediate product to obtain a semi-finished cathode plate;
and welding a negative tab 23 on the semi-finished product of the negative plate to obtain the battery negative plate 2.
In this embodiment, different amounts of the suspending agent glue solution are added in different times during the preparation process of the negative electrode slurry, and the method has the advantages that: adding a part of suspending agent glue solution in the early stage to make the slurry in a sticky state, wherein the stirring shearing force of the slurry is larger, and the material particles are fully dispersed by matching with a certain rotating speed and time; and the suspending agent glue solution is added in the later period, and the powdered main material is fully kneaded with the suspending agent, the cathode binder and the cathode conductive agent in cooperation with certain rotating speed and time, so that the cathode slurry has a good dispersing effect, a stable slurry system is formed, and the consistency of the lithium ion battery is favorably improved.
Preferably, when different amounts of the suspending agent glue solution are added in different times, the mixing rotating speed is different, so that the material particles can be fully and quickly dispersed.
Further, the present embodiment also provides a lithium ion battery, which includes a battery case (not shown), a battery positive plate 1, a first diaphragm (not shown), a second diaphragm (not shown), an electrolyte and the battery negative plate 2, where the battery positive plate 1, the battery negative plate 2, the first diaphragm, the second diaphragm and the electrolyte are all disposed in the battery case, and the battery positive plate 1, the battery negative plate 2, the first diaphragm and the second diaphragm are all immersed in the electrolyte, the battery negative plate 2 is located between the battery positive plate 1 and the battery case, the first diaphragm is disposed between the battery positive plate 1 and the battery negative plate 2, and the second diaphragm is disposed between the battery case and the battery negative plate 2. According to the lithium ion battery provided by the embodiment of the invention, the battery negative plate 2 is adopted, so that the stability and the cycle life of the lithium ion battery are improved.
Preferably, the battery positive plate 1 comprises a positive metal substrate 11, a positive lug 13 in conductive connection with the positive metal substrate 11 and a battery positive coating 12 coated outside the positive metal substrate 11, the components of the battery positive coating 12 comprise a positive active material, a positive binder and a positive conductive agent, and the battery positive coating comprises a positive active material, a positive binder and a positive conductive agentMedian particle diameter D of positive electrode active material50Is 7mm +/-3 microns. Compared with the positive active material with the median particle size of 12 microns +/-1 micron in the prior art, the method achieves the purpose of effectively reducing the median particle size D of the positive active material50Thereby being beneficial to improving the stability of the positive active material of the lithium ion battery in a high-voltage 4.35V lithium removal state. Median diameter (also called median diameter) D of positive electrode active material50Specifically, the physical meaning of the particle size of the positive electrode active material is that the particle size is 50% larger than the particle size of the positive electrode active material and 50% smaller than the particle size of the positive electrode active material.
Preferably, the positive active material includes a ternary material LiNixMnyCozO2Particles and LiNi coated on the ternary materialxMnyCozO2A coating layer outside the particles, wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z is 1.0;
the coating layer comprises MgO and Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of (1).
The battery positive electrode coating 12 provided in this embodiment adopts a ternary material LiNi coated with a coating layerxMnyCozO2The particles can be used as positive active material and can use ternary material LiNixMnyCozO2The characteristic of small particle size effectively reduces the median particle size of the positive active material, so that the change of the particle volume of the positive active material in a lithium removal state at a high voltage of 4.35V is small, and the structural stability of the lithium ion battery is improved. Ternary material LiNixMnyCozO2During the charging process of the particles, along with the continuous release of lithium ions, the valence of the internal metal element is correspondingly increased if the ternary material LiNi is not usedxMnyCozO2The particles adopt any protective measures, and the ternary material LiNixMnyCozO2The particles are easy to react with the electrolyte to cause the dissolution of metal ions, thereby leading to the LiNi of the ternary materialxMnyCozO2The structure of the particles is destroyed; and with the continuous rise of the charging voltage, the dissolving speed of the metal ions is also continuously accelerated, and the embodiment of the invention coats MgO and Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of these coating substances in a ternary material LiNixMnyCozO2A protective layer is formed on the surface of the particles, so that the dissolution of metal ions in the anode is avoided, the stable structure of the anode material is ensured, the metal ions are not dissolved, the stability of the structure of the anode active substance can be kept in the charging and discharging process, and the cycle life of the lithium ion battery is effectively prolonged.
Preferably, x is 0.8, y is 0.1, and z is 0.1; or x is 0.7, y is 0.1, and z is 0.2; or x is 0.5, y is 0.2 and z is 0.3, and the ternary material LiNi prepared by adopting the valuesxMnyCozO2The particles can better meet the performance requirements of the positive active material, and the median particle size of the positive active material can be smaller. Of course, in a specific application, the values of x, y and z are not limited to only values, as long as the following relational expressions are satisfied: x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z is 1.0.
Preferably, the specific surface area of the positive electrode active material is 0.4m2/g～0.8m2(ii) in terms of/g. Here, the specific surface area of the positive electrode active material is large, which is advantageous for improving the structural stability of the positive electrode active material. The specific surface area of the positive electrode active material specifically means the total area per unit mass of the positive electrode active material.
Preferably, the tap density of the positive electrode active material is 1.6g/cm3～2.4g/cm3. The tap density of the positive electrode active material specifically refers to the mass per unit volume measured after the positive electrode active material is tapped.
Preferably, the gram capacity of the positive electrode active material is 155mAh/g to 175 mAh/g. The gram capacity of the positive electrode active material means a ratio of an electric capacity that the positive electrode active material can release to a mass of the positive electrode active material.
Preferably, the cladding layer comprises at least one of the metal oxides, i.e. the cladding layer comprises MgO, Al2O3、ZrO2、TiO2Thus, the structural stability of the single crystal ternary material is further improved through the protection of the oxide.
Preferably, the cladding layer comprises Al2O3And ZrO2(ii) a And Al in the coating layer2O3And ZrO2The weight portions of the positive active material are respectively 0.8% +/-0.5% and 0.5% +/-0.3%, namely the positive active material has 0.8% +/-0.5% of Al2O3And 0.5% of. + -. 0.3% of ZrO2。
As a preferred embodiment of this embodiment, Al is included in the cladding layer2O3And ZrO2The weight portions of the positive active material are respectively 0.8 percent and 0.5 percent.
Preferably, the components of the battery positive electrode coating 12 include the following components in parts by weight:
95.0 to 98.2 percent of positive active material;
1.0 to 5.0 percent of positive electrode binder;
0.3 to 5.0 percent of positive electrode conductive agent.
Here, the components of the battery positive electrode coating 12 are optimally designed, which is beneficial to improving the capacity of the lithium ion battery and the adhesive force of the battery positive electrode coating 12, thereby being beneficial to improving the long cycle life and the safety and reliability of the lithium ion battery.
Preferably, the battery positive electrode coating 12 comprises the following components in parts by weight: 97.2% of positive electrode active material; 1.3% of a positive electrode binder; 1.5% of positive electrode conductive agent; or, the battery positive electrode coating 12 comprises the following components in parts by weight: 98.2% of positive electrode active material; 1.0% of positive electrode binder; 0.8% of positive electrode conductive agent; or, the battery positive electrode coating 12 comprises the following components in parts by weight: 95.0% of positive electrode active material; 2.5% of a positive electrode binder; 2.5 percent of positive electrode conductive agent. Test tests show that the battery anode coating 12 adopts the components in parts by weight, and the effects of improving the capacity of the lithium ion battery, improving the adhesive force of the battery anode coating 12, improving the cycle performance of the lithium ion battery and improving the safety performance of the lithium ion battery are obvious.
Preferably, the positive electrode conductive agent is at least one of conductive graphite, conductive carbon black, carbon nanotubes, carbon fibers, carbon nanotubes and graphene. The positive electrode conductive agent adopts at least one of the substances, which is beneficial to reducing the internal resistance of the lithium ion battery and improving the capacity, the cycle performance and the rate performance of the lithium ion battery.
Preferably, the positive electrode binder is at least one of polyvinylidene fluoride (PVDF) and polyvinyl alcohol (PVA). The two binders are adopted as the positive binder, so that the battery positive coating 12 can have good adhesion performance.
Preferably, the thickness of the positive electrode metal substrate 11 is 12 μm + -2 μm, and the thickness of the battery positive electrode sheet 1 is 123 μm + -5 μm. Thus, the battery positive plate 1 is beneficial to exerting the best performance of the positive active material on the premise of ensuring the smaller size. Of course, the thickness of the positive electrode metal substrate 11 and the thickness of the battery positive electrode sheet 1 are not limited thereto in specific applications.
Preferably, the positive electrode metal substrate 11 is an aluminum foil, which can meet the conductive performance requirement of the battery positive electrode plate 1, and has light weight and low cost. Of course, the material of the positive electrode metal substrate 11 is not limited thereto in specific applications.
Preferably, the method for manufacturing the positive electrode sheet 1 of the battery of the present embodiment includes the steps of:
adding the positive adhesive into a nitrogen-methyl pyrrolidone solvent according to the weight part ratio in the battery positive coating 12, and mixing to prepare a positive adhesive glue solution with the solid content of 5-10%, wherein the solid content of the positive adhesive glue solution specifically refers to the mass percentage of the residual part of the positive adhesive glue solution in the total amount after drying;
adding a positive conductive agent into the positive bonding glue solution according to the weight part ratio in the battery positive coating 12 to prepare a positive conductive glue solution;
adding a positive active substance into the positive conductive glue solution according to the weight part ratio in the battery positive coating 12, and adding a nitrogen-methyl pyrrolidone solvent to prepare positive slurry with the solid content of 40-75%;
coating the positive electrode slurry on a positive electrode metal substrate 11 to prepare a positive electrode coating intermediate product;
drying and curing the anode coating intermediate product to dry and cure the anode slurry into the battery anode coating 12 to obtain an anode cured intermediate product;
sequentially rolling and cutting the positive electrode curing intermediate product to obtain a semi-finished positive electrode plate;
and welding the positive tab 13 on the semi-finished product of the positive plate to obtain the battery positive plate 1.
Preferably, the concentration of the lithium salt of the electrolyte is 1.1mol/L to 1.3 mol/L. Here, the electrolyte may form a high voltage electrolyte.
Preferably, the electrolyte contains at least one of LiFSI lithium bis (fluorosulfonyl) imide and TMSP tris (trimethylsilane) phosphate. LiFSI (fluorosulfonyl) imide lithium and TMSP (trimethylsilane) can stabilize the interface between the battery positive plate 1 and the electrolyte under the high-voltage condition, and reduce the dissolution of metal ions on the surface of an electrode and the oxidative decomposition of the electrolyte, so that the stability of the battery positive plate 1 is improved, and the cycle life of the lithium ion battery is further prolonged.
More preferably, the electrolyte includes a solvent, a lithium salt, a first additive and a second additive, the solvent is a mixture of EC (ethylene carbonate), DMC (dimethyl carbonate), EMC (ethyl methyl carbonate), and the first additive includes FEC (fluoroethylene carbonate), DTD (ethylene sulfate), lidfo (lithium difluoroborate). In the specific production process, a battery positive plate 1, a battery negative plate 2, a first diaphragm and a second diaphragm are wound to form a battery roll core, the battery roll core is placed in a battery shell, high-voltage electrolyte is injected, and a solvent of the electrolyte and a first additive can form a stable SEI film on the battery negative plate 2; by adding second additives LiFSI (fluorosulfonyl) imide lithium and TMSP (trimethylsilane), the interface between the battery positive plate 1 and the electrolyte is stabilized under the condition of high voltage, and the dissolution of metal ions on the surface of an electrode and the oxidative decomposition of the electrolyte are reduced, so that the stability of the battery positive plate 1 is improved, and the cycle life of the lithium ion battery is prolonged.
As a preferred embodiment of this embodiment, the ratio of the solvent in the electrolyte is EC: DMC: EMC 1: 1: and 8, the lithium salt concentration is 1.2mol/L, the first additive content is 3% FEC, 0.5% DTD and 0.5% LiDFOB, and the second additive comprises LiFSI and TMSP.
Preferably, the lithium ion battery provided by the embodiment is a 4.35V high-voltage 2400mAh long-cycle cylindrical lithium ion battery, the charge cut-off voltage of the lithium ion battery is 4.35V, and compared with the 4.2V charge cut-off voltage in the prior art, the gram capacity of the positive active material is increased by 8%, the battery capacity is increased by 8%, the energy density is increased by 8% -9%, the lithium ion battery can realize a voltage range of 2.75V-4.35V, the charge and discharge cycle of 0.5CA current is 1000 weeks, and the capacity retention rate is not less than 80%.
The lithium ion battery provided by the embodiment has the following remarkable effects:
1) the artificial graphite particles coated with the hard carbon material are used as the negative active material, so that the hard carbon material layer can form a protective layer outside the artificial graphite particles to prevent solvent molecules of electrolyte from being embedded into a negative graphite structure layer, and the hard carbon material has the characteristic of good conductivity, thereby being beneficial to further improving the cycle performance of the lithium ion battery and finally effectively prolonging the cycle life of the lithium ion battery.
2) Using the coated single crystal ternary material LiNixMnyCozO2The particles are used as positive electrode active material, so that the prepared positive electrode active material D50Since the particle size is small, i.e., 7 ± 3 μm, the positive electrode active material particles have a small volume change and a stable structure in a lithium-removed state at a high voltage of 4.35V.
3) The hard carbon material with better cycle performance is coated outside the artificial graphite to be used as a negative active material, so that the cycle life of the lithium ion battery is prolonged, in addition, the surface defects of graphite particles are few, and a stable electrode/electrolyte interface film (namely an SEI film) can be formed.
4) In the present case, the negative electrode binder is preferably polyacrylate. Polyacrylic acid has a long-chain structure similar to SBR, so the binding property of the polyacrylic acid is equivalent to that of SBR; at the same time, it possesses a carboxyl structure, possibly with Li+Formation of lithium carboxylate groups, contributing to the enhancement of Li+The conductivity of the battery is improved, so that the resistance of the pole piece and the internal resistance of the battery are smaller, and the cycle performance of the battery is improved.
5) The mechanical strength and the electrochemical stability of the electrode are improved by optimizing and adjusting the formula, the coating surface density and the rolling compaction degree of the materials of the anode coating and the cathode coating 22, so that the cycle life of the lithium ion battery is prolonged.
6) The high-voltage electrolyte is used, the concentration of lithium salt of the electrolyte is 1.1-1.3 mol/L, special additives LiFSI and TMSP are added in the electrolyte formula, and the dissolution of metal ions on the surface of an electrode and the oxidative decomposition of the electrolyte are reduced under the high-voltage condition, so that the cycle stability of the anode is improved, and the cycle life of the battery is prolonged.
7) The positive and negative electrode slurry formula and pole piece process design parameters reach the optimal values, and the material formula and the pole piece process are suitable, so that the material can exert the optimal performance, and the comprehensive performance of the battery is improved.
As a preferred embodiment of this embodiment, the manufacturing process of the lithium ion battery and the performance test result thereof are as follows:
the tap density is selected to be 1.6g/cm3～2.4g/cm3The specific surface area is 0.4m2/g～0.8m24-8 μm of D50, 155 mAh/g-175 mAh/g of gram capacity, and the single crystal ternary material LiNi after external coating treatmentxMnyCozO2The particles serve as a positive electrode active material. The tap density is 0.9g/cm3～1.2g/cm3The specific surface area was 0.8m2/g～1.2m211-18 mu m of D50, 340-380 mAh/g of gram capacity, and small-particle-size artificial graphite powder coated with hard carbon material as a negative active material. Polyacrylate with both binding property and excellent conductivity is selected as the negative electrode binder.
Mixing 1.3 wt% of polyvinylidene fluoride and N-methyl pyrrolidone solvent to prepare a positive electrode binder glue solution with solid content of 5-10%; then adding 1.5 wt% of carbon nano tube conductive agent for mixing to prepare anode conductive glue solution; adding 97.2 wt% of positive active material into the conductive glue solution, adding N-methyl pyrrolidone solvent, and mixing to obtain positive slurry with solid content of 60-75%; coating the positive electrode slurry on a metal aluminum foil with the thickness of 12 mu m, drying at the temperature of 80-120 ℃, and rolling into a battery positive electrode sheet 1 with the thickness of about 123 mu m.
Adding 1.3 wt% of CMC dry powder into deionized water, and mixing to obtain suspending agent glue solution with solid content of 2.0% for later use; the preparation method comprises the steps of mixing a soft carbon material coating layer, 95.0% of small-particle-size artificial graphite powder, 1.5% of Super P dry powder and 50% -70% of suspending agent glue solution in percentage by weight, mixing at a certain rotating speed for a certain time, adding the rest of the suspending agent glue solution and 2.2% of polyacrylic emulsion in percentage by weight, mixing at a certain rotating speed for a certain time, adding a proper amount of deionized water for continuous mixing to prepare negative electrode slurry with the solid content of 40% -55%, coating the negative electrode slurry on a metal copper foil with the thickness of 8 microns, drying at the temperature of 80-120 ℃, and rolling to form the battery negative electrode sheet 2 with the thickness of about 147 microns.
Cutting a battery anode plate and a battery cathode plate into long strips, reserving a metal aluminum foil welding lug at 2/5 of the length of the battery anode plate 1, reserving a section of metal copper foil welding lug at one end of the battery cathode plate 2, winding a polyethylene film diaphragm with the thickness of 16 mu m, the battery cathode plate 2 and the battery anode plate 1 into a cylindrical winding core, welding an anode lug 13 led out from the battery anode plate 1 at a cap aluminum sheet connecting sheet by laser welding, spot-welding a cathode lug 23 led out from the battery cathode plate 2 at the bottom of a steel shell of a battery shell, fully baking the cylindrical winding core, injecting 5.6-5.8g of electrolyte, sealing, placing in an environment of 25-35 ℃ for 48h, and using a specific forming process to form an activated battery to form a stable SEI film on the interface of an internal electrode and the electrolyte, namely assembling the 2400mAh lithium ion battery with high voltage long circulation.
Performing constant-current constant-voltage charging (cutoff current is 0.01CA) on the lithium ion battery by using 0.5CA current until the voltage is 4.35V, and then discharging the battery by using 0.2CA constant current until the voltage is 2.75V, wherein the discharge capacity of the battery is more than or equal to 2400 mAh; when the charge-discharge cycle test is carried out on the lithium ion battery by a 0.5CA constant-current constant-voltage charge and 0.5CA constant-current discharge system with the voltage range of 2.75-4.35V, the battery capacity at the 1000 th cycle is more than or equal to 80 percent of the initial capacity.
Example two:
the battery negative electrode coating 22, the battery negative electrode sheet 2, the method for manufacturing the battery negative electrode sheet 2, and the lithium ion battery provided in this embodiment are mainly different from those of the first embodiment in terms of the positive electrode active material, and are specifically embodied as follows:
in this embodiment, the positive electrode active material includes a ternary material LiNixMnyCozO2Particles and LiNi doped in the ternary materialxMnyCozO2Doping elements in particles and LiNi coated on the ternary materialxMnyCozO2A coating layer outside the particles, wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z is 1.0;
the doping element comprises at least one of Al and F;
the coating layer comprises MgO and Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of (1).
The battery positive electrode coating 12 provided in this embodiment adopts a ternary material LiNi with a doped element inside and a coating layer outsidexMnyCozO2The particles can be used as positive active material and can use ternary material LiNixMnyCozO2The characteristic of small particle size effectively reduces the median particle size of the positive active material, so that the change of the particle volume of the positive active material in a lithium removal state at a high voltage of 4.4V is small, and the structural stability of the lithium ion battery is improved.
If the doping element comprises Al element, the cation mixed-arrangement degree in the ternary material crystal can be reduced, so that the crystal structure tends to be stable in a high-voltage state; if the doping elements comprise F elements, the surface of the material can react with the electrolyte to form a film with smaller impedance (namely an SEI film of the anode), so that the resistance of the anode plate of the battery can be reduced, the internal resistance of the lithium ion battery is further reduced, and the cycle performance of the lithium ion battery is improved.
Ternary material LiNixMnyCozO2During the charging process of the particles, along with the continuous release of lithium ions, the valence of the internal metal element is correspondingly increased if the ternary material LiNi is not usedxMnyCozO2The particles adopt any protective measures, and the ternary material LiNixMnyCozO2The particles are easy to react with the electrolyte to cause the dissolution of metal ions, thereby leading to the LiNi of the ternary materialxMnyCozO2The structure of the particles is destroyed; and with the continuous rise of the charging voltage, the dissolving speed of the metal ions is also continuously accelerated, and the embodiment of the invention coats MgO and Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of these coating substances in a ternary material LiNixMnyCozO2A protective layer is formed on the surface of the particles, so that the dissolution of metal ions in the anode is avoided, the stable structure of the anode material is ensured, the metal ions are not dissolved, the stability of the structure of the anode active substance can be kept in the charging and discharging process, and the cycle life of the lithium ion battery is effectively prolonged.
Preferably, the doping elements include Al and F, wherein Al accounts for 0.5% ± 0.3% (in the present embodiment, 0.5% is preferable), and F accounts for 0.9% ± 0.4% (in the present embodiment, 0.9% is preferable) of the positive electrode active material. Herein, Al and F elements are co-doped, wherein the doping of 0.5% of Al element reduces the cation mixed-arranged degree in the ternary material crystal, so that the crystal structure tends to be stable in a high-voltage state; 0.9 percent of F element is doped, so that the surface of the material reacts with electrolyte to form a film (namely an SEI film) with smaller impedance, thereby reducing the resistance of a battery anode plate 1, further reducing the internal resistance of the lithium ion battery, being beneficial to improving the cycle performance of the lithium ion battery, and on the basis, 0.8 percent of 0.5 percent of Al is coated on the ternary material2O3And 0.2% ZrO2The corrosion of the electrolyte to the battery anode plate material can be prevented, and the occurrence of adverse side reaction is avoided, so that the cycle life of the battery anode plate 1 material is prolonged.
Preferably, doping elements Al and F are doped in the ternary material LiNixMnyCozO2The intragranular method comprises the following steps: at least one of Al and F and a ternary material LiNixMnyCozO2Mixing, lithiating, sintering, pulverizing under proper conditions of temperature, time and atmosphere to obtain Al and F doped ternary material LiNixMnyCozO2And (3) granules. After doping modification, doped Al and F ions enter the ternary material LiNixMnyCozO2Inside the particles, thereby improving the performance of the positive electrode active material.
Preferably, the lithium ion battery provided by the embodiment is a 4.4V high-voltage 2400mAh long-cycle cylindrical lithium ion battery, the charge cut-off voltage of the lithium ion battery is 4.4V, and compared with the 4.2V charge cut-off voltage in the prior art, the capacity of the lithium ion battery is improved by 14% -17%, the lithium ion battery can realize the charge and discharge cycle of 0.5CA current for 400 weeks within the voltage range of 2.75V-4.4V, and the capacity retention rate is not less than 80%.
As a preferred embodiment of this embodiment, the manufacturing process of the lithium ion battery and the performance test result thereof are as follows:
the tap density is selected to be 1.6g/cm3～2.4g/cm3The specific surface area is 0.4m2/g～0.8m2D50 is 4-8 μm, gram capacity is 155 mAh/g-175 mAh/g, Al and F elements are doped in the interior, and the exterior is coated with the single crystal ternary material LiNixMnyCozO2The particles serve as a positive electrode active material. The tap density is 0.9g/cm3～1.2g/cm3The specific surface area was 0.8m2/g～1.2m211-18 mu m of D50, 340-380 mAh/g of gram capacity, and small-particle-size artificial graphite powder coated with hard carbon material as a negative active material. Polyacrylic acid with both adhesive property and excellent conductivity is selected as the negative electrode adhesive.
Mixing 1.3 wt% of polyvinylidene fluoride and N-methyl pyrrolidone solvent to prepare a positive electrode binder glue solution with solid content of 5-10%; then adding 1.5 wt% of carbon nano tube conductive agent for mixing to prepare anode conductive glue solution; adding 97.2 wt% of positive active material into the conductive glue solution, adding N-methyl pyrrolidone solvent, and mixing to obtain positive slurry with solid content of 60-75%; coating the positive electrode slurry on a metal aluminum foil with the thickness of 12 mu m, drying at the temperature of 80-120 ℃, and rolling into a battery positive electrode sheet 1 with the thickness of about 123 mu m.
Adding 1.3 wt% of CMC dry powder into deionized water, and mixing to obtain suspending agent glue solution with solid content of 2.0% for later use; the preparation method comprises the steps of mixing a soft carbon material coating layer, 95.0% of small-particle-size artificial graphite powder, 1.5% of Super P dry powder and 50% -70% of suspending agent glue solution in percentage by weight, mixing at a certain rotating speed for a certain time, adding the rest of the suspending agent glue solution and 2.2% of polyacrylic emulsion in percentage by weight, mixing at a certain rotating speed for a certain time, adding a proper amount of deionized water for continuous mixing to prepare negative electrode slurry with the solid content of 40% -55%, coating the negative electrode slurry on a metal copper foil with the thickness of 8 microns, drying at the temperature of 80-120 ℃, and rolling to form the battery negative electrode sheet 2 with the thickness of about 147 microns.
Cutting a battery anode plate and a battery cathode plate into long strips, reserving a metal aluminum foil welding lug at 2/5 of the length of the battery anode plate 1, reserving a section of metal copper foil welding lug at one end of the battery cathode plate 2, winding a polyethylene film diaphragm with the thickness of 16 mu m, the battery cathode plate 2 and the battery anode plate 1 into a cylindrical winding core, welding an anode lug 13 led out from the battery anode plate 1 at a cap aluminum sheet connecting sheet by laser welding, spot-welding a cathode lug 23 led out from the battery cathode plate 2 at the bottom of a steel shell of a battery shell, fully baking the cylindrical winding core, injecting 5.6-5.8g of electrolyte, sealing, placing in an environment of 25-35 ℃ for 48h, and using a specific forming process to form an activated battery to form a stable SEI film on the interface of an internal electrode and the electrolyte, namely assembling the 2400mAh lithium ion battery with high voltage long circulation.
Performing constant-current constant-voltage charging (cutoff current is 0.01CA) on the lithium ion battery by using 0.5CA current until the voltage is 4.4V, and then discharging the battery by using 0.2CA constant current until the voltage is 2.75V, wherein the discharge capacity of the battery is more than or equal to 2400 mAh; when the charge-discharge cycle test is carried out on the lithium ion battery by a 0.5CA constant-current constant-voltage charge and 0.5CA constant-current discharge system with the voltage range of 2.75-4.4V, the battery capacity at the 400 th week is more than or equal to 80 percent of the initial capacity.
In addition to the above-mentioned LiNi in the ternary materialxMnyCozO2Increased doping within the particlesIn addition to Al and F, the battery negative electrode coating 22, the battery negative electrode sheet 2, the manufacturing method of the battery negative electrode sheet 2, and other design means of the lithium ion battery provided in this embodiment can be optimally designed with reference to the first embodiment, and will not be described in detail herein.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The battery negative electrode coating is characterized by comprising a negative electrode active material, a negative electrode conductive agent, a suspending agent and a negative electrode binder, wherein the negative electrode active material comprises artificial graphite particles and a hard carbon material layer coated outside the artificial graphite particles.
2. The battery negative electrode coating of claim 1, comprising the following components in parts by weight: 94.0-97.0 percent of negative electrode active material, 0.2-2.2 percent of negative electrode conductive agent, 1.2-2.0 percent of suspending agent and 1.4-2.4 percent of negative electrode binder.
3. The battery negative electrode coating of claim 2, wherein the battery negative electrode coating comprises the following components in parts by weight: 95.0% of negative electrode active material, 1.5% of negative electrode conductive agent, 1.3% of suspending agent and 2.2% of negative electrode binder; or,
the battery negative electrode coating comprises the following components in parts by weight: 94.0% of negative electrode active material, 1.6% of negative electrode conductive agent, 2.0% of suspending agent and 2.4% of negative electrode binder; or,
the battery negative electrode coating comprises the following components in parts by weight: 97.0% of negative electrode active material, 0.3% of negative electrode conductive agent, 1.2% of suspending agent and 1.5% of negative electrode binder.
4. The battery negative electrode coating of any of claims 1 to 3, wherein the hard carbon material layer is made of carbon black; and/or the presence of a gas in the atmosphere,
the negative electrode conductive agent comprises at least one of conductive carbon black, conductive graphite and carbon nano tubes; and/or the presence of a gas in the atmosphere,
the negative electrode binder comprises at least one of sodium carboxymethylcellulose, styrene butadiene rubber, polyacrylic acid and sodium alginate; and/or the presence of a gas in the atmosphere,
the suspending agent is sodium carboxymethyl cellulose.
5. The battery negative plate comprises a negative metal substrate, a negative lug in conductive connection with the negative metal substrate and a negative coating coated outside the negative metal substrate, and is characterized in that the negative coating adopts the battery negative coating as claimed in any one of claims 1 to 4.
6. The method for manufacturing the negative electrode sheet for the battery according to claim 5, comprising the steps of:
adding the suspending agent dry powder into deionized water, and mixing to obtain suspending agent glue solution;
mixing a negative electrode active substance, a negative electrode conductive agent and 50-70% of the suspending agent glue solution to prepare a negative electrode semi-finished product slurry;
adding a negative electrode binder and the rest of the suspending agent glue solution into the negative electrode semi-finished product slurry, mixing, adding deionized water, and continuously mixing to prepare a negative electrode slurry;
coating the negative electrode slurry on a negative electrode metal substrate to obtain a negative electrode coating intermediate product;
drying and curing the cathode coating intermediate product to dry and cure the cathode slurry into a battery cathode coating, thereby preparing a cathode cured intermediate product;
sequentially rolling and cutting the anode cured intermediate product to obtain a semi-finished cathode plate;
and welding negative electrode lugs on the semi-finished product of the negative electrode plate to obtain the battery negative electrode plate.
7. The lithium ion battery is characterized by comprising a battery shell, a battery positive plate, a first diaphragm, a second diaphragm, electrolyte and the battery negative plate according to claim 5, wherein the battery positive plate, the battery negative plate, the first diaphragm, the second diaphragm and the electrolyte are all arranged in the battery shell, the battery positive plate, the battery negative plate, the first diaphragm and the second diaphragm are all immersed in the electrolyte, the battery negative plate is located between the battery positive plate and the battery shell, the first diaphragm is arranged between the battery positive plate and the battery negative plate, and the second diaphragm is arranged between the battery shell and the battery negative plate.
8. The lithium ion battery of claim 7, wherein the battery positive plate comprises a positive metal substrate, a positive tab conductively connected with the positive metal substrate, and a battery positive coating coated on the positive metal substrate, the components of the battery positive coating comprise a positive active material, a positive binder and a positive conductive agent, and the positive active material comprises a positive active material, a positive binder and a positive conductive agentMedian particle diameter D of50Is 7mm +/-3 microns.
9. The lithium ion battery of claim 8, wherein the positive active material comprises a ternary material LiNixMnyCozO2Particles and LiNi coated on the ternary materialxMnyCozO2A coating layer outside the particles, wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z is 1.0;
the coating layer comprises MgO and Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of; or,
the components of the battery anode coating comprise an anode active substance, an anode binder and an anode conductive agent, wherein the anode active substance comprises a ternary material LiNixMnyCozO2Particles and LiNi doped in the ternary materialxMnyCozO2Doping elements in particles and LiNi coated on the ternary materialxMnyCozO2A coating layer outside the particles, wherein x is more than or equal to 0.5 and less than or equal to 0.8, y is more than or equal to 0.1 and less than or equal to 0.3, z is more than or equal to 0.1 and less than or equal to 0.3, and x + y + z is 1.0;
the doping element comprises at least one of Al and F;
the coating layer comprises MgO and Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of (1).
10. The lithium ion battery of any of claims 7 to 9, wherein the electrolyte has a lithium salt concentration of 1.1 to 1.3 mol/L; and/or the presence of a gas in the atmosphere,
the electrolyte contains at least one of LiFSI and TMSP.
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