CN109817906A - Anode coating, battery anode slice and lithium ion battery - Google Patents
Anode coating, battery anode slice and lithium ion battery Download PDFInfo
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Abstract
The present invention is suitable for field of lithium ion battery, disclose anode coating, battery anode slice and lithium ion battery, wherein, the component of anode coating includes positive active material, positive electrode binder, positive conductive agent, and positive active material includes ternary material LiNixMnyCozO2Particle is doped in ternary material LiNixMnyCozO2Intragranular doped chemical and it is coated on ternary material LiNixMnyCozO2Clad outside particle, wherein 0.5≤x≤0.8,0.1≤y≤0.3,0.1≤z≤0.3, x+y+z=1.0；Doped chemical includes at least one of Al, F；Clad includes MgO, Al2O3、ZrO2、TiO2、AlPO4、AlF3、LiAlO2、LiTiO2At least one of.The present invention is using inside doped with Al and/or F and the external ternary material LiNi being coated with coating layerxMnyCozO2Particle as a positive electrode active material, improves the stability of positive active material structure, extends the cycle life of lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a battery anode coating, a battery anode plate and a lithium ion battery.
Background
The positive plate of the lithium ion battery generally comprises a positive metal substrate and a positive coating coated outside the positive metal substrate, wherein the components of the positive coating generally comprise a positive active material, a positive binder and a positive conductive agent.
In the existing lithium ion battery, the median particle size of the positive active material is generally within the range of 12 microns +/-1 micron, and the volume change of the particles of the positive active material is large in a lithium removal state when the voltage is high and 4.4V, so that the structural stability of the lithium ion battery is poor, and the cycle life of the lithium ion battery is not prolonged.
Disclosure of Invention
The invention aims to provide a battery anode coating, which aims to solve the technical problem that the structural stability of a lithium ion battery is poor due to large volume change of anode active material particles in a lithium-removing state of the conventional lithium ion battery at a high voltage of 4.4V.
In order to achieve the purpose, the invention provides the following scheme: the battery anode coating comprises the components of 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).
Alternatively, 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＝0.5，y＝0.2，z＝0.3。
optionally, the median particle diameter D of the positive electrode active material507mm +/-3 mu m; and/or the presence of a gas in the atmosphere,
the tap density of the positive electrode active material is 1.6g/cm3～2.4g/cm3(ii) a And/or the presence of a gas in the atmosphere,
the front partSpecific surface area of the electrode active material 0.4m2/g～0.8m2(ii)/g; and/or the presence of a gas in the atmosphere,
the gram capacity of the positive active substance is 155 mAh/g-175 mAh/g; and/or the presence of a gas in the atmosphere,
the positive electrode conductive agent is at least one of conductive graphite, conductive carbon black, carbon fiber, carbon nano tube and graphene; and/or the presence of a gas in the atmosphere,
the positive electrode binder is at least one of polyvinylidene fluoride and polyvinyl alcohol.
Optionally, the coating comprises at least one of a metal oxide.
Optionally, the cladding layer comprises Al2O3And ZrO2And Al in the coating layer2O3And ZrO2The weight portions of the positive active material are respectively 0.8% +/-0.5% and 0.5% +/-0.3%; and/or the presence of a gas in the atmosphere,
the doping elements comprise Al and F, wherein the Al accounts for 0.5% +/-0.3% of the weight of the positive active substance, and the F accounts for 0.9% +/-0.4% of the weight of the positive active substance.
Optionally, the components of the battery positive electrode coating comprise 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.
Optionally, the battery positive electrode coating 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 anode coating 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 anode coating 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.
The invention also provides a battery positive plate, which comprises a positive metal substrate, a positive lug electrically connected with the positive metal substrate and a positive coating coated outside the positive metal substrate, wherein the positive coating adopts the battery positive coating.
A third object of the present invention is to provide a lithium ion battery, which includes a battery case, a battery negative plate, a first diaphragm, a second diaphragm, an electrolyte and the battery positive 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 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 ternary material LiNi which is internally doped with Al and/or F and externally coated with a coating layer is adoptedxMnyCozO2The particles are used as positive electrode active material, so that on the one hand, the ternary material LiNi can be usedxMnyCozO2The 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 improvedSex; on the other hand, if the doping element comprises an Al element, the cation mixed-discharging degree in the ternary material crystal can be reduced, so that the crystal structure tends to be stable in a high-voltage state, and if the doping element comprises an F element, the surface of the material can react with the electrolyte to form a film (namely an anode SEI film) with smaller impedance, so that the resistance of a battery anode plate can be reduced, the internal resistance of the lithium ion battery is further reduced, and the cycle performance of the lithium ion battery is favorably improved; on the other hand, the material can be coated on the ternary material LiNixMnyCozO2The coating outside the particles forms a protective layer, so that the specific surface area of the positive active material can be increased, the coating can prevent positive metal ions from being dissolved in the charging process, the stability of the structure of the positive active material can be kept in the charging and discharging process, and finally the cycle life of the lithium ion battery is effectively prolonged.
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 positive plate of a battery provided by an embodiment of the invention;
fig. 2 is a schematic structural diagram of a negative electrode sheet 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.
As shown in fig. 1-2, the positive electrode coating 12 of the battery provided by the embodiment of the invention comprises positive active material, positive binder and positive conductive agent, wherein the positive active material comprises ternary material LiNixMnyCozO2Particles and LiNi doped in ternary materialxMnyCozO2Doping elements in the particles and LiNi coated in 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 anode coating 12 provided by the embodiment of the invention adopts a ternary material LiNi with doped elements 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,in the embodiment of the invention, MgO and Al are coated2O3、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 median particle diameter D of the positive electrode active material50Is 7mm +/-3 mu m, and compared with the positive active material with the median particle size of 12 mu m +/-1 mu m in the prior art, the median particle size D of the positive active material is effectively reduced50Thereby being beneficial to improving the stability of the anode active material of the lithium ion battery in a high-voltage 4.4V 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 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 a unit mass of the positive electrodeThe total area of the active substance.
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% + -0.3% 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 doping elements comprise Al and F, wherein Al accounts for 0.5% + -0.3% of the weight of the positive electrode active substance, and F accounts for 0.9% + -0.4% of the weight of the positive electrode active substance. The Al and F elements are co-doped, wherein the doping of 0.5 +/-0.3% of the Al element reduces the cation mixed arrangement degree in the ternary material crystal, so that the crystal structure tends to be stable in a high-voltage state; f element of 0.9% +/-0.4% is doped, so that the surface of the material reacts with the electrolyte to form a film (namely a positive SEI film) with smaller impedance, and the resistance of the battery positive plate 1 is reduced, and the resistance is further reducedThe internal resistance of the lithium ion battery is beneficial to improving the cycle performance of the lithium ion battery, and on the basis, the ternary material is coated with 0.8 percent of Al2O3And 0.5% ZrO2The corrosion of the electrolyte to the material of the battery positive plate 1 can be prevented, and the occurrence of adverse side reactions is avoided, so that the cycle life of the material of the battery positive plate 1 is prolonged.
As a preferred embodiment of this embodiment, the doping element Al accounts for 0.5% by weight of the positive electrode active material, and the doping element F accounts for 0.9% by weight of the positive electrode active material.
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 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 fiber, carbon nanotube 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.
According to the battery anode coating provided by the embodiment of the invention, the ternary material is subjected to a mode of combining doping modification and coating modification, so that the structural stability of the battery anode coating under high voltage is improved, and the generation of side reactions of a battery anode plate is reduced, so that the battery anode plate material can obtain high voltage and long-cycle performance.
Further, the embodiment of the invention also provides a battery positive plate 1, which comprises a positive metal substrate 11, a positive lug 13 in conductive connection with the positive metal substrate 11 and a positive coating coated outside the positive metal substrate 11, wherein the positive coating adopts the battery positive coating 12. According to the battery positive plate 1 provided by the embodiment of the invention, the battery positive coating 12 is adopted, so that the stability of the structure of a positive active material can be kept in the charging and discharging processes, and the cycle life of a lithium ion battery is effectively prolonged.
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 according to the embodiment of the present invention 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.
Further, the embodiment of the invention also provides a lithium ion battery, which comprises a battery shell, a battery negative plate 2, a first diaphragm, a second diaphragm, electrolyte and the battery positive plate 1, wherein the battery positive plate 1, the battery negative plate 2, the first diaphragm, the second diaphragm and the electrolyte are all arranged in the battery shell, 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 positioned between the battery positive plate 1 and the battery shell, the first diaphragm is arranged between the battery positive plate 1 and the battery negative plate 2, and the second diaphragm is arranged between the battery shell and the battery negative plate 2. According to the lithium ion battery provided by the embodiment of the invention, the battery positive plate 1 is adopted, so that the stability, the safety and the reliability of the lithium ion battery are improved, and the cycle life of the lithium ion battery is prolonged.
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 battery negative plate 2 comprises a negative metal substrate 21, a negative tab 23 electrically connected with the negative metal substrate 21, and a negative coating 22 coated outside the negative metal substrate 21, wherein the negative coating 22 comprises a negative active material, a negative conductive agent, a suspending agent and a negative binder, and the negative active material comprises artificial graphite particles and a soft carbon material coated outside the artificial graphite particles. The artificial graphite is made of amorphous carbon material N2Graphitizing at high temperature (> 2500 ℃) in the atmosphere. The soft carbon is an easily graphitized carbon material, such as petroleum coke, asphalt and the like, has good compatibility with the electrolyte, and forms a compact SEI film to prevent a solvent from being embedded into graphite, thereby prolonging the cycle life of the battery. Here, the substance formed by coating the soft carbon material with good cycle performance outside the artificial graphite particles is used as the negative electrode active material, so that the cycle life of the battery is prolonged. The anode coating 22 is formed by curing the anode slurry.
Preferably, the 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. Test tests show that the 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 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 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 negative electrode coating 22 and the negative electrode metal substrate 21 have good adhesion performance.
Preferably, the suspending agent is sodium carboxymethylcellulose (CMC). The suspending agent is sodium carboxymethylcellulose, so that the cathode conductive agent and the cathode active substance can be suspended in the prepared cathode slurry, and meanwhile, the adhesive force between the components of the cathode coating 22 and the adhesive force between the cathode coating 22 and the cathode metal substrate 21 after the battery cathode sheet 2 is dried can be improved by utilizing the adhesive capacity of the sodium carboxymethylcellulose and the synergistic effect of the cathode adhesive.
Preferably, the preparation method of the battery negative electrode sheet 2 comprises the following steps: adding the suspending agent dry powder into deionized water, and mixing to prepare suspending agent glue solution for later use; mixing the small-particle-size negative active material, the negative conductive agent and 50-70% of suspending agent glue solution, and mixing at a certain rotation speed for a certain time; and adding all the rest of the suspending agent glue solution and the negative electrode binder, mixing at a certain rotating speed for a certain time, adding a proper amount of deionized water, continuously mixing to prepare negative electrode slurry, coating the negative electrode slurry on a negative electrode metal substrate 21, drying at the temperature of 80-120 ℃, rolling, cutting and processing to prepare the battery negative electrode sheet 2. Here, in the preparation process of the cathode slurry, different amounts of the suspending agent glue solution are added in a plurality of times, and different rotating speeds are adjusted at the same time, 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.
Of course, in particular applications, the negative electrode slurry may be prepared by the following method as an alternative embodiment: adding the suspending agent dry powder into deionized water, and mixing to prepare suspending agent glue solution for later use; mixing the small-particle-size negative active material, the negative conductive agent and all the suspending agent glue solution, adding the negative binder after mixing at a certain rotating speed for a certain time, adding a proper amount of deionized water, and continuously mixing to prepare the negative slurry.
Preferably, the lithium ion battery provided by the embodiment of the invention 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, 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-discharge cycle of 0.5CA current for 600 weeks within the voltage range of 2.75V-4.4V, and the capacity retention rate is more than or equal to 80%.
The lithium ion battery provided by the embodiment of the invention has the following remarkable effects:
1) 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 4.4V.
2) The soft 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.
3) 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.
4) 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.
5) 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 implementation of the embodiment of the present invention, 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, Al and F elements doped in the interior 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 soft carbon material as a negative active material.
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 SBR 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 600 th week is more than or equal to 80 percent of the initial capacity.
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 anode coating is characterized by comprising the components of 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).
2. The battery positive electrode coating of claim 1,
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＝0.5，y＝0.2，z＝0.3。
3. the battery positive electrode coating according to claim 1 or 2,
the median particle diameter D of the positive electrode active material507mm +/-3 mu m; and/or the presence of a gas in the atmosphere,
the tap density of the positive electrode active material is 1.6g/cm3～2.4g/cm3(ii) a And/or the presence of a gas in the atmosphere,
the specific surface area of the positive electrode active material was 0.4m2/g～0.8m2(ii)/g; and/or the presence of a gas in the atmosphere,
the gram capacity of the positive active substance is 155 mAh/g-175 mAh/g; and/or the presence of a gas in the atmosphere,
the positive electrode conductive agent is at least one of conductive graphite, conductive carbon black, carbon fiber, carbon nano tube and graphene; and/or the presence of a gas in the atmosphere,
the positive electrode binder is at least one of polyvinylidene fluoride and polyvinyl alcohol.
4. The battery positive electrode coating of claim 1 or 2, wherein the cladding layer comprises at least one of a metal oxide.
5. The battery positive electrode coating of claim 4, wherein the cladding layer comprises Al2O3And ZrO2And Al in the coating layer2O3And ZrO2The weight portions of the positive active material are respectively 0.8% +/-0.5% and 0.5% +/-0.3%; and/or the presence of a gas in the atmosphere,
the doping elements comprise Al and F, wherein the Al accounts for 0.5% +/-0.3% of the weight of the positive active substance, and the F accounts for 0.9% +/-0.4% of the weight of the positive active substance.
6. The battery positive electrode coating according to claim 1 or 2, wherein the components of the battery positive electrode coating comprise 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.
7. The battery positive electrode coating of claim 6,
the battery anode coating 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 anode coating 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 anode coating 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.
8. The battery positive plate comprises a positive metal substrate, a positive lug in conductive connection with the positive metal substrate and a positive coating coated outside the positive metal substrate, and is characterized in that the positive coating adopts the battery positive coating as claimed in any one of claims 1 to 7.
9. The lithium ion battery is characterized by comprising a battery shell, a battery negative plate, a first diaphragm, a second diaphragm, electrolyte and the battery positive plate according to claim 8, 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 positioned 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.
10. The lithium ion battery of claim 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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