CN111129447A - Ternary positive electrode material for long-cycle-life lithium storage battery and preparation method thereof - Google Patents

Ternary positive electrode material for long-cycle-life lithium storage battery and preparation method thereof Download PDF

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CN111129447A
CN111129447A CN201911048420.6A CN201911048420A CN111129447A CN 111129447 A CN111129447 A CN 111129447A CN 201911048420 A CN201911048420 A CN 201911048420A CN 111129447 A CN111129447 A CN 111129447A
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ternary
solid electrolyte
inorganic solid
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positive electrode
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许晓雄
刘冀鹏
张永龙
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Zhejiang Funlithium New Energy Tech Co Ltd
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Abstract

The invention relates to a ternary anode material, and discloses a ternary anode material for a long-cycle-life lithium storage battery and a preparation method thereof, wherein an alumina precursor solution is used as a source of alumina in a shell layer, the alumina precursor solution is added with a ternary material and inorganic solid electrolyte microcrystals, ammonia water is added, the mixture is heated and stirred to form gel, and then the gel is further sintered to obtain powder of the ternary anode material, wherein particles of the powder comprise an inner core and a shell layer, the inner core is a nickel-cobalt-manganese ternary material, and the shell layer is formed by mixing alumina and the inorganic solid electrolyte microcrystals; the inorganic solid electrolyte microcrystal is embedded and fixed in the alumina, and forms an ion conduction channel singly or in combination; the ion conduction channel is communicated with the outer surface of the shell layer and the outer surface of the inner core; the ternary cathode material has good conductivity, and when the ternary cathode material is used as a cathode in a lithium storage battery, the cycle performance, the rate capability and the safety performance of the mixed solid-liquid electrolyte lithium storage battery and the all-solid-state lithium storage battery are improved.

Description

Ternary positive electrode material for long-cycle-life lithium storage battery and preparation method thereof
Technical Field
The invention relates to a ternary cathode material, in particular to a ternary cathode material for a long-cycle-life lithium storage battery and a preparation method thereof.
Background
The lithium storage battery industry is an important component of the new energy industry. In recent years, with the rapid development of new energy industries, higher and higher requirements are put forward on the safety and cycle life performance of lithium storage batteries, and the technical directions of mixed solid-liquid electrolyte lithium storage batteries, all-solid lithium storage batteries and the like are more and more paid attention by the academic and industrial fields. The mixed solid-liquid electrolyte lithium accumulator and the all-solid-state lithium accumulator are the same as all the existing batteries, and both comprise three important components: a positive electrode, an electrolyte, and a negative electrode.
The conventional anode is mostly made of a solid-state anode material, wherein the anode material which is widely applied mainly comprises a traditional lithium iron phosphate anode material and a nickel-cobalt-manganese (NCM) ternary anode material which is used more currently. The nickel-cobalt-manganese ternary cathode material has higher energy density due to high nickel content, so that the nickel-cobalt-manganese ternary cathode material is more and more popular in the market and the market share is continuously expanded. However, compared with the traditional lithium iron phosphate cathode material, the nickel content of the nickel-cobalt-manganese ternary cathode material is high, so that the lithium insertion capacity is high, and certain defects are brought. The potential of the nickel-cobalt-manganese (NCM) ternary cathode material after lithium removal is high, wherein transition metal is converted into a high valence state and is easy to react with liquid electrolyte and partial solid electrolyte such as sulfide solid electrolyte and organic polymer solid electrolyte, so that electrolyte degradation and transition metal element dissolution are caused, potential safety hazards are formed, and the safety performance of the lithium storage battery is reduced.
In order to solve the problems, in the prior art, aluminum oxide is coated on the ternary positive electrode material particles, and the aluminum oxide with relatively stable chemical property provides a layer of protection for the ternary material particles, so that the direct contact between the ternary material and an electrolyte is reduced, the oxidation effect of the positive electrode material on the electrolyte under the high-voltage condition is reduced, the stability of the ternary material is further improved, and the cycle performance and the safety performance of the ternary material in the use process of a lithium storage battery are improved. In addition, in order to ensure the protection effect of the aluminum oxide, the technology has high requirements on the integrity and compactness of the aluminum oxide coated with the ternary cathode material particles.
Therefore, the technology in the prior art is optimized and improved, for example, a vapor deposition method is mostly adopted to deposit a complete and compact aluminum oxide coating layer on the outer surface of the ternary cathode material particle in the using process, even the surface of the ternary cathode material particle is firstly subjected to corona discharge treatment and then is deposited with aluminum oxide by the vapor deposition method, so that the adhesive force of the aluminum oxide coating layer on the surface of the ternary cathode material particle is improved.
However, while the technology adopts a complete and compact alumina coating layer to coat and protect the ternary cathode material particles, the conductivity of the ternary cathode is greatly reduced due to poor electronic conductivity and ionic conductivity of alumina, and the rate capability of the lithium storage battery is reduced. Meanwhile, the molecular structure of the aluminum oxide causes irreversible lithium intercalation after the aluminum oxide is used in a lithium storage battery for a long time. For the technology, the ternary cathode material particles are completely coated with alumina, and after irreversible lithium intercalation occurs, the ternary cathode material particles obviously affect the cycle performance of the lithium storage battery.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a ternary cathode material for a long-cycle-life lithium storage battery, which has good conductivity and can improve the cycle performance, rate capability and safety performance of a mixed solid-liquid electrolyte lithium storage battery and an all-solid-state lithium storage battery.
The technical purpose of the invention is realized by the following technical scheme:
the utility model provides a long cycle life is ternary cathode material for lithium battery, ternary cathode material is the anodal powder composition of ternary of nucleocapsid structure, and it includes ternary cathode powder includes kernel and shell, the kernel is nickel cobalt manganese ternary, the shell is including mixed aluminium oxide and inorganic solid state electrolyte micrite, inorganic solid state electrolyte micrite is inorganic oxide solid state electrolyte or fast ion conductor solid state electrolyte, inorganic solid state electrolyte micrite gomphosis is fixed in the aluminium oxide in the shell, just inorganic solid state electrolyte micrite alone or the combination structure ion switches on the passageway, the ion switches on the surface of passageway intercommunication shell and the surface of kernel.
By adopting the technical scheme, the crystal grain of the nickel-cobalt-manganese ternary material is taken as the inner core, and the outer side of the crystal grain is coated by mixing inorganic solid electrolyte microcrystal and alumina to form a shell layer, so that the ternary cathode powder particle with a mixed core-shell structure is formed. The inorganic solid electrolyte microcrystal has good ionic conductivity, and the inorganic solid electrolyte microcrystal in the shell layer is embedded and fixed to form an ion conduction channel communicating the outer side surface of the shell layer and the outer surface of the core, so that the lithium ion conductivity of the shell layer is improved.
Meanwhile, the inorganic solid electrolyte microcrystal is embedded with the aluminum oxide in a mixed mode and is fixed on the surface of the inner core in a compounding mode to form a shell layer, the strength of the shell layer formed after the inorganic solid electrolyte microcrystal and the aluminum oxide are mixed is enhanced, the effect of inhibiting the volume change of the ternary material in the charging and discharging process is enhanced, the ternary material and the solid electrolyte in the anode are prevented from being separated from each other in an interface mode, the interface bonding performance and the thermal stability inside the anode are further enhanced, and the conductivity, the cycle performance and the safety performance of the anode are improved.
When the ternary positive electrode material is used as a positive electrode in a lithium storage battery, the cycle performance, rate capability and safety performance of the mixed solid-liquid electrolyte lithium storage battery and the all-solid-state lithium storage battery are improved.
The invention is further configured to: the diameter of the inner core is 3-10 mu m, and the thickness of the shell layer is 0.2-1 mu m.
By adopting the technical scheme, the specific gravity of the nickel-cobalt-manganese ternary material in the ternary cathode material is reduced due to the excessively thick thickness of the shell layer, the gram capacity of the ternary cathode material is reduced, the rate capability of the ternary cathode material is reduced, the path of electron conduction and ion conduction is increased due to the excessively thick thickness of the shell layer, and the conductivity and the rate capability of the material are reduced. The shell layer is thin, so that the inorganic solid electrolyte microcrystal is required to have small grain size, the preparation difficulty of the inorganic solid electrolyte microcrystal is increased, the inorganic solid electrolyte microcrystal with small grain size is difficult to disperse in an alumina precursor solution and is easy to be combined with an aluminum hydroxide colloid to agglomerate, and the inorganic solid electrolyte microcrystal is poor in distribution and adhesion on nickel-cobalt-manganese ternary material powder particles. Therefore, when the thickness of the mixed shell layer formed by the inorganic solid electrolyte microcrystal and the aluminum oxide is 0.2-1 mu m, the conductivity, the rate capability and the cycle performance of the mixed shell layer are good.
The invention is further configured to: the ratio of the particle size of the inorganic solid electrolyte microcrystal to the shell thickness is 0.65-1.
Through adopting above-mentioned technical scheme, the formation distribution condition of ion conduction channel is influenced to the granularity of inorganic solid state electrolyte micrite and the ratio of shell thickness, and here inorganic solid state electrolyte micrite is close with shell thickness, so the ion conduction channel mostly comprises solitary inorganic solid state electrolyte micrite, when reducing the interface impedance between the inorganic solid state electrolyte micrite, make the ion conduction channel keep stable in structure when the anodal volume of charge-discharge process changes, improve anodal cyclicity and stability, improve lithium battery's security performance.
And the granularity of the inorganic solid electrolyte microcrystal is similar to the thickness of the shell layer, so that the inorganic solid electrolyte microcrystal is independently embedded in the shell layer direction, the compactness and the uniform distribution of the aluminum oxide in the shell layer are improved, the strength of the shell layer is improved, and the effect of the shell layer is ensured.
The invention is further configured to: the mass ratio of the inorganic solid electrolyte microcrystal to the aluminum oxide in the shell layer is 1-2.
By adopting the technical scheme, the inorganic solid electrolyte microcrystal in the shell layer is taken as an important and large-proportion component, and the inorganic solid electrolyte microcrystal is selected as an inorganic oxide solid electrolyte or a fast ion conductor solid electrolyte in the application, so that the solid electrolyte has better stability to a liquid electrolyte, a sulfide solid electrolyte and the like, and compared with a ternary material and a solid point electrolyte, the solid electrolyte has better compatibility and stability, so that the inorganic solid electrolyte microcrystal in the shell layer can protect the ternary material while achieving ion conduction, and the stability of the ternary material is improved.
Meanwhile, the inorganic solid electrolyte microcrystal occupying a large proportion is mixed with the aluminum oxide to form the shell layer, so that the structural strength of the shell layer can be enhanced, the limiting effect of the shell layer on the volume change of the core is further enhanced, and the contribution of the anode prepared from the ternary anode material in the improvement of the cycle performance of the lithium storage battery is further improved.
The invention is further configured to: the inorganic solid electrolyte microcrystal is Li1+xAlxGe2-x(PO4)3(LAGP)、Li1+xAlxTi2-x(PO4)3(LATP) (x is more than 0 and less than or equal to 0.5).
By adopting the technical scheme, Li1+xAlxGe2-x(PO4)3(LAGP) and Li1+xAlxTi2-x(PO4)3The preparation process of (LATP) (x is more than 0 and less than or equal to 0.5) is simple and easy to obtain, and the lithium ion conductivity is higher at room temperature, so that the production cost can be reduced by using the two inorganic solid electrolyte microcrystals, and better product performance can be obtained at the same time.
The invention is further configured to: the inner core is made of nickel-cobalt-manganese ternary single crystal material.
By adopting the technical scheme, the core is a nickel-cobalt-manganese single crystal ternary material, compared with a ternary polycrystalline anode material, the ternary single crystal anode material has the advantages of long cycle life and good volume recovery in the charging and discharging processes of the lithium storage battery, so that the shell layer has good bonding performance, the single crystal is favorable for aluminum oxide to distribute and wrap the core, the compactness in the shell layer is uniformly distributed, the interface effect is weakened, and the conductivity and the cycle performance of the anode material are improved.
Aiming at the defects in the prior art, the second purpose of the invention is to provide the preparation method of the ternary cathode material for the long-cycle-life hybrid solid-liquid lithium storage battery, which is used for improving the conductivity of the cathode and preparing the cycle performance of the lithium storage battery of the cathode by using the ternary cathode material.
The technical purpose of the invention is realized by the following technical scheme:
a method for preparing a ternary cathode material for a long-cycle-life lithium storage battery comprises the following steps,
s1: ball-milling the nickel-cobalt-manganese ternary material by using a ball mill until the particle size reaches 3-10 mu m to obtain nickel-cobalt-manganese ternary material powder;
s2: ball-milling the inorganic solid electrolyte by a ball mill until the particle size reaches less than 1 mu m to obtain inorganic solid electrolyte microcrystal;
s3: mixing an aluminum oxide precursor and water to prepare an aluminum oxide precursor solution, wherein the aluminum oxide precursor is one or more of aluminum acetate, aluminum nitrate and aluminum sulfate, and the concentration of aluminum element in the aluminum oxide precursor solution is 3-10 wt%;
s4: adding the nickel-cobalt-manganese ternary material powder prepared by the step S1 and the inorganic solid electrolyte microcrystal prepared by the step S2 into the alumina precursor solution prepared by the step S3, and then adding citric acid and glycol to form a mixed suspension, wherein the mass fractions of the citric acid and the glycol in the suspension are both 0.5-1 wt%; adding ammonia water into the suspension, adjusting the pH value to 9-10, heating and stirring at 80 ℃ after dropwise adding is completed until precursor gel is formed, wherein the mass parts of the nickel-cobalt-manganese ternary material in the precursor gel are 70-94, the mass parts of the inorganic solid electrolyte microcrystal are 3-20, and the mass parts of the aluminum oxide obtained by equivalent conversion of aluminum hydroxide are 3-10;
s5: and sintering the precursor gel prepared in the step S4 at 150-200 ℃ for 2h in an air atmosphere, and then sintering at 500-700 ℃ for 4h in a nitrogen atmosphere to obtain the ternary cathode material for the lithium storage battery with long cycle life.
By adopting the technical scheme, the preparation method takes the alumina precursor solution as the source of the alumina in the shell layer. When the nickel-cobalt-manganese ternary material powder and the inorganic solid electrolyte microcrystal are added into the alumina precursor solution, citric acid and glycol are also added, and the citric acid and the glycol can form a complex compound to complex aluminum-containing ions in the alumina precursor solution, so that aluminum hydroxide colloidal particles form hysteresis after ammonia water is added, the particle size of the aluminum hydroxide colloidal particles is refined, and the distribution of the aluminum hydroxide colloidal particles is more uniform.
Meanwhile, in the preparation method, the ground inorganic solid electrolyte microcrystal is used as the source of the inorganic solid electrolyte in the shell layer, and the inorganic solid electrolyte microcrystal and the nickel-cobalt-manganese ternary material powder are matched according to a specific proportion and added into the alumina precursor solution. The inorganic solid electrolyte microcrystal is bonded with aluminum hydroxide colloidal particles in an alumina precursor solution, under the bonding action of the aluminum hydroxide colloidal particles attached to the surfaces of the nickel-cobalt-manganese ternary material powder particles, the inorganic solid electrolyte microcrystal and the aluminum hydroxide colloidal particles are uniformly distributed and attached to and fixed on the surfaces of the nickel-cobalt-manganese ternary material powder particles, and finally, the ternary anode material with the core-shell structure is obtained after sintering, wherein the bonding strength between the middle shell layer and the inner core is good, and the inorganic solid electrolyte microcrystal and the alumina are uniformly distributed. Compared with the mixture of the inorganic solid electrolyte and the aluminum oxide on the microcosmic scale, the ion conduction channel or the ion conduction network structure constructed by the inorganic solid electrolyte microcrystal in the shell layer of the ternary cathode material finally obtained by sintering in the method has stable structure and good conductivity, solves the problem that the inorganic solid electrolyte and the aluminum oxide cannot be mixed to obtain a compact shell layer at different precipitation temperatures in vapor deposition, effectively improves the conductivity of the shell layer, and improves the conductivity of the cathode and the cycle performance of the lithium storage battery.
Aiming at the defects in the prior art, the invention also provides the application of the ternary cathode material for the lithium storage battery with the cycle life in a solid-state lithium storage battery and a solid-liquid mixed lithium storage battery.
In conclusion, the invention has the following beneficial effects:
1. the crystal grain of the nickel-cobalt-manganese ternary material is used as a core, and the outer side of the crystal grain is coated by mixing inorganic solid electrolyte microcrystal and alumina to form a shell layer, so that ternary anode powder particles with a mixed core-shell structure are formed. And the inorganic solid electrolyte microcrystal in the shell layer is embedded and fixed to form an ion conduction channel for communicating the outer side surface of the shell layer with the outer surface of the core, so that the lithium ion conductivity of the shell layer is improved. Meanwhile, the inorganic solid electrolyte microcrystal and the aluminum oxide are mixed and embedded to form a shell layer, the strength and the effect of inhibiting the volume change of the ternary material in the charging and discharging process are enhanced, the interface bonding performance and the thermal stability inside the anode are enhanced, and the conductivity, the cycling performance and the safety performance of the anode are improved.
2. According to the preparation method of the ternary cathode material, citric acid and glycol are added while the ternary material and the inorganic solid electrolyte microcrystal are added into the alumina precursor solution, and the citric acid and the glycol can form a complex to complex aluminum ions in the alumina precursor solution, so that aluminum hydroxide colloidal particles are formed after ammonia water is added, the particle size of the aluminum hydroxide colloidal particles is refined, the distribution of the aluminum hydroxide colloidal particles is more uniform, and the compactness of aluminum peroxide in a shell layer is improved.
3. The application discovers that the inorganic solid electrolyte microcrystal is embedded and fixed on the shell layer formed in the aluminum oxide, the ion conduction channel or the ion conduction network constructed by the inorganic solid electrolyte microcrystal has stable structure and good conductivity, the problem that the inorganic solid electrolyte and the aluminum oxide cannot be mixed to obtain a compact shell layer at different precipitation temperatures in vapor deposition is solved, the conductivity of the shell layer is effectively improved, and the conductivity of the anode and the cycle performance of the lithium storage battery are improved.
Description of the drawings:
FIG. 1 is a comparison graph of XRD data for a solid electrolyte, alumina, ternary material, and a ternary positive electrode material for a long cycle life lithium battery of the present application;
FIG. 2 is a first SEM image of a ternary cathode material for a long-cycle-life lithium secondary battery of the present application;
fig. 3 is a SEM image of the ternary cathode material for a long cycle life lithium secondary battery according to the present application.
Detailed Description
In the case of the example 1, the following examples are given,
a ternary anode material for a long-cycle-life lithium storage battery is composed of ternary anode powder, wherein particles of the ternary anode powder comprise an inner core and a shell layer.
The diameter of the inner core is 3-10 mu m, the inner core is made of a nickel-cobalt-manganese ternary material, and the nickel-cobalt-manganese ternary single crystal material is preferably selected. The nickel cobalt manganese ternary material can be made by self or purchased directly from the market, and is a product sold by fir shares company.
The thickness of the shell layer is 0.2-1 mu m, the shell layer is formed by mixing compact aluminum oxide and inorganic solid electrolyte microcrystals, and the mass ratio of the inorganic solid electrolyte microcrystals to the aluminum oxide is 1-2. Wherein the inorganic solid electrolyte crystallites are inorganicAn organic oxide solid electrolyte or a fast ion conductor solid electrolyte, which may be made available by itself or purchased directly from the market. The preferable inorganic solid electrolyte crystallite here is Li1+xAlxGe2-x(PO4)3(LAGP)、Li1+xAlxTi2-x(PO4)3(LATP) (0 < x ≦ 0.5), preferably LAGP, which is a product of Zhejiang lithium New energy science and technology Limited.
The inorganic solid electrolyte microcrystal in the shell layer is embedded and fixed on the aluminum oxide, the ratio of the granularity of the inorganic solid electrolyte microcrystal to the thickness of the shell layer is 0.625-1, an ion conduction channel or an ion conduction network is constructed in the shell layer by the inorganic solid electrolyte microcrystal, and the ion conduction channel or the ion conduction network is communicated with the outer surface of the shell layer and the outer surface of the core.
A method for preparing a ternary cathode material for a long-cycle-life lithium storage battery comprises the following steps,
s1: ball-milling the nickel-cobalt-manganese ternary material until the particle size is 5 mu m to obtain nickel-cobalt-manganese ternary material powder;
s2: ball-milling the inorganic solid electrolyte until the particle size is 0.5 mu m to obtain inorganic solid electrolyte microcrystal;
s3: mixing an alumina precursor and water to prepare an alumina precursor solution, wherein the alumina precursor is aluminum acetate, and Al is contained in the alumina precursor solution3+The concentration is 8 wt%;
s4: adding nickel-cobalt-manganese ternary material powder and inorganic solid electrolyte microcrystal into an alumina precursor solution, wherein the mass ratio of the nickel-cobalt-manganese ternary material powder to the inorganic solid electrolyte microcrystal to the alumina precursor solution is 80:15:100, adding citric acid and ethylene glycol after mixing, and uniformly mixing to form a suspension, wherein the mass fraction of the citric acid in the suspension is 1 wt%, and the mass fraction of the ethylene glycol in the suspension is 0.5 wt%; adding ammonia water into the turbid liquid, adjusting the pH value to 9-10, heating and stirring at 80 ℃ after dropwise adding is completed until precursor gel is formed, wherein the precursor gel comprises the following ternary materials in percentage by mass: inorganic solid electrolyte crystallites: alumina 80:13: 8;
s5: and sintering the precursor gel prepared in the step S4 at 200 ℃ for 2h in an air atmosphere, and then sintering the precursor gel at 700 ℃ for 4h in a nitrogen atmosphere to obtain the ternary cathode material for the lithium storage battery with the long cycle life.
XRD detection is carried out on the ternary cathode material for the long-cycle-life lithium storage battery obtained in example 1, the detection result is compared with the ternary material of inorganic solid electrolyte microcrystal, aluminum oxide and nickel cobalt manganese, and the result is shown in figure 1, wherein NCM is the ternary material of nickel cobalt manganese, and L is the inorganic solid electrolyte microcrystal. And SEM images were taken as shown in fig. 2 and 3.
In the examples 2 to 6, the following examples were carried out,
a ternary cathode material for a long-cycle-life lithium storage battery is prepared by adjusting parameters in a preparation method based on example 1, wherein the specific parameters are shown in the table I. And simultaneously, carrying out stripping-element determination test on the ternary cathode powder. Measuring the concentration of Al element under different stripping depth conditions; and taking the stripping thickness when the concentration of the Al element is lower than the detection limit as the thickness of the shell layer.
Table one.
Figure BDA0002254696930000071
Comparative examples 1 to 3 were also provided.
In the comparative example 1,
the ternary positive electrode material was prepared according to the preparation method described in example 1 of publication No. CN108493478A, and the preparation method was as follows:
(1) LiNi lithium nickel cobalt manganese oxide0.6Co0.2Mn0.2O2Preparing a precursor of the ternary cathode material:
109.620g of nickel nitrate Ni (NO)3)258.211g of cobalt nitrate Co (NO)3)2·6H2O, 35.790g manganese nitrate Mn (NO)3)2Adding the mixture into 700ml of isopropanol, and then dropwise adding 1mol/L ammonium bicarbonate solution into the isopropanol until the pH value of the solution is 10-12. Then placing the mixture into a polytetrafluoroethylene reaction kettle for solvothermal reaction at 150 ℃ for 12h, and then filtering and washing the mixture to obtain a precursor of the ternary cathode material.
(2) Preparing a precursor of the aluminum hydroxide-coated ternary cathode material:
adding the ternary positive electrode material precursor into 42.0ml of 0.01mol/L aluminum sulfate solution, stirring to form uniform dispersion, slowly dropwise adding sodium bicarbonate solution while stirring until no gas is generated, washing, and filtering to obtain Al (OH)3A coated ternary precursor.
(3) Preparing the anode material with a three-layer core-shell structure by adopting a wet method, a sol-gel method and one-step calcination:
6.071g of lithium acetate, 0.636g of tetrabutyl titanate and 0.124g of aluminum nitrate (Al (NO) were added3)3·9H2O), 0.879g of tributyl phosphate and 2g of citric acid are added into water, then the pH is adjusted to 6-8 to form gel, and then glycol solution is added into the gel to properly dilute the sol, and the sol is continuously stirred. Then, the above-mentioned Al (OH) was added thereto3And heating the coated ternary precursor at 180 ℃, wherein the outside of the coated ternary precursor is coated with Li, Ti, Al and phosphate radical gel, and some lithium ions can penetrate into the inside of the coated ternary precursor and be embedded into the ternary precursor or the anode material.
And (3) placing the gel at 900 ℃ for aerobic calcination treatment for 4h to obtain the anode material with the three-layer core-shell structure.
In a comparative example 2,
based on comparative example 1, the difference is that the ternary cathode material precursor obtained in step (1) of comparative example 1 is ground and sieved to obtain 5 +/-0.5 mu m powder for use in step (2).
In a comparative example 3,
a ternary positive electrode material for a long-cycle-life lithium storage battery is prepared by the following steps,
s1: ball-milling the obtained ternary material by using a ball mill until the particle size reaches 5 mu m to obtain nickel-cobalt-manganese ternary material powder;
s2: mixing an alumina precursor and water to prepare an alumina precursor solution, wherein the alumina precursor is aluminum acetate, and Al is contained in the alumina precursor solution3+The concentration is 8 wt%;
s3: adding the nickel-cobalt-manganese ternary material powder prepared by the step S1 into the alumina precursor solution prepared by the step S2, adding citric acid and glycol, and uniformly mixing to form a suspension, wherein the mass fraction of the citric acid in the suspension is 1 wt%, and the mass fraction of the glycol in the suspension is 0.5 wt%; and adding ammonia water into the suspension, adjusting the pH value to 9-10, and heating and stirring at 80 ℃ after dropwise addition is completed until precursor gel is formed.
S4: and (3) sintering the precursor gel prepared in the step S3 at 200 ℃ for 2h in an air atmosphere, and then sintering the precursor gel at 700 ℃ for 4h in a nitrogen atmosphere to obtain the ternary cathode material.
In a comparative example 4,
the ternary positive electrode material for the long-cycle-life lithium storage battery is based on the embodiment 1, and is characterized in that the nickel-cobalt-manganese ternary material used for the inner core is a polycrystalline material.
In a comparative example 5,
based on the embodiment 1, the ternary cathode material for the lithium storage battery with long cycle life is characterized in that the consumption of inorganic solid electrolyte microcrystals and Al in an alumina precursor solution are increased in equal proportion3+The concentration is adjusted to adjust the shell thickness, and the shell thickness of the prepared ternary cathode material is 2 +/-0.2 mu m.
In a comparative example 6,
based on example 1, the ternary cathode material for the long-cycle-life lithium storage battery is characterized in that the crystallite size of the inorganic solid electrolyte is 50nm, and Al in an alumina precursor solution3+The concentration is 3 wt%, and the shell thickness of the prepared ternary cathode material is 0.1 μm.
In a comparative example 7,
a ternary positive electrode material for a long cycle life lithium secondary battery, based on example 1, characterized in that the inorganic solid electrolyte has a crystallite size of 0.2 μm.
In a comparative example 8,
based on the embodiment 1, the ternary cathode material for the lithium storage battery with long cycle life is characterized in that the content of alumina precursor in solution is increasedAl3+Concentration, the mass ratio of inorganic solid electrolyte microcrystals in precursor gel to aluminum oxide equivalently converted from aluminum hydroxide in the preparation process of the prepared ternary cathode material is 1.
In a comparative example 9,
based on the embodiment 1, the ternary cathode material for the lithium storage battery with long cycle life is characterized in that Al in an alumina precursor solution is improved3+Concentration, the mass ratio of the organic solid electrolyte microcrystal in the precursor gel to the aluminum oxide equivalently converted from the aluminum hydroxide in the preparation process of the prepared ternary cathode material is 2.
The following electrochemical performance test was performed on examples 1 to 6 and comparative examples 1 to 9:
pressing the ternary cathode material into a sheet-shaped lithium ion solid electrolyte with the diameter of 10mm and the thickness of 1mm under the conditions that the water content is less than 10ppm and the pressure is 200 MPa. Then, the direct current polarization test was performed with carbon as a blocking electrode. And calculating the conductivity according to the intersection point of the impedance spectrum curve and the Z' axis and the direct current polarization curve. The results are shown in Table 2.
Table 2.
Figure BDA0002254696930000091
As can be seen from table 2, as compared with the test results of examples 1 to 6 and comparative example 3, the conductivity of the ternary cathode material obtained in examples 1 to 6 is better than that of comparative example 3, so that compared with the ternary cathode material obtained by simply coating an alumina shell layer, the conductivity of the ternary cathode material obtained by mixing and coating alumina and a solid electrolyte by using a gel method is improved.
As can be seen from table 2, by comparing the test results of examples 1 to 6 with comparative examples 1 and 2, the conductivity of the ternary cathode material obtained in examples 1 to 6 is superior to that of comparative examples 1 and 3, and an ion conduction channel or an ion conduction network with good conductivity is effectively constructed in the ternary cathode material obtained by mixing and coating aluminum oxide and a solid electrolyte by using a gel method, so that the conductivity of the ternary cathode material obtained in the present application is significantly improved.
As can be seen from table 2, according to the test results of comparative example 1 and comparative examples 5 and 6, the thickness of the shell layer in the ternary cathode material of the present application is too thick, which causes the path of electron transfer and ion conduction to increase, and reduces the conductivity and rate capability of the material. The shell layer is thin, so that the inorganic solid electrolyte microcrystal is required to have small grain size, the preparation difficulty of the inorganic solid electrolyte microcrystal is increased, the inorganic solid electrolyte microcrystal with small grain size is difficult to disperse in an alumina precursor solution and is easy to be combined with an aluminum hydroxide colloid to agglomerate, and the inorganic solid electrolyte microcrystal is poor in distribution and adhesion on nickel-cobalt-manganese ternary material powder particles. Therefore, the thickness of the shell layer in the application is preferably 0.2-1 μm.
Solid electrolyte lithium accumulator
A solid electrolyte lithium secondary battery includes a positive plate, a negative plate, a solid electrolyte membrane disposed between the positive plate and the negative plate, an outer packaging membrane, a positive terminal, and a negative terminal.
The positive plate consists of a positive current collector and a positive layer. The thickness of the positive current collector is 7-9 μm, and the positive current collector is generally an aluminum foil or a copper foil, where the aluminum foil is an aluminum current collector, and the thickness of the aluminum current collector is 8 μm.
The positive electrode layer is obtained by mixing a positive electrode material, a conductive agent and a binder into slurry according to the mass ratio of 86:7:7, coating the slurry on an aluminum current collector and drying the slurry. The post-drying degree of the positive electrode layer is 50 to 250 μm, here 200 μm.
The anode material is a ternary anode material. The conductive agent in the positive electrode layer is one or more of conductive carbon black (SP), Carbon Nanotubes (CNTs) and graphene, and the conductive carbon black (SP) is used here. The binder in the positive electrode layer is one or more of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC) and styrene butadiene latex (SBR), and the binder is polyvinylidene fluoride (PVDF).
The negative plate consists of a negative current collector and a negative layer. The negative current collector is copper, namely a copper current collector, and the thickness of the copper current collector is 8 mu m.
The negative electrode layer is formed by sequentially mixing a negative electrode material, a negative electrode electrolyte, a conductive agent and a binder according to a mass ratio of 85: 5: 5: 5 mixing the mixture into slurry, coating the slurry on a copper current collector, and drying to obtain the copper current collector, wherein the thickness of a dried negative electrode layer is 80-180 mu m, and the thickness is 120 mu m.
The cathode material is a common graphite material, and the common graphite material is one or more of artificial graphite or natural graphite. The conductive agent in the negative electrode is one or more of conductive carbon black (SP), Carbon Nanotubes (CNTs) and graphene, and the conductive carbon black (SP) is used here. The binder in the negative electrode is one or more of polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC) and styrene butadiene latex (SBR), wherein the polyvinylidene fluoride (PVDF) is used.
The solid electrolyte membrane was a PEO solid electrolyte membrane, and its thickness was 10 μm.
The preparation method of the solid electrolyte lithium storage battery comprises the following steps:
A. and mixing the positive electrode material, the conductive agent and the binder into slurry according to the mass ratio of 86:7:7, coating the slurry on an aluminum current collector with the size of 8 mu m, and drying to obtain the positive electrode plate.
B. The anode material, the solid electrolyte, the conductive agent and the binder are sequentially mixed according to the mass ratio of 85: 5: 5: 5, mixing into slurry, coating the slurry on a copper current collector with the diameter of 0.8 mu m, and drying to obtain the negative plate.
C. And (3) forming by a hot pressing method, laminating and pressing the positive plate prepared in the step A, the solid electrolyte membrane and the negative plate prepared in the step B to obtain a prefabricated battery core, mounting a positive terminal and a negative terminal, and coating an aluminum plastic film to obtain the solid electrolyte lithium storage battery, wherein the solid electrolyte membrane is a PEO solid electrolyte membrane with the thickness of 15 mu m.
Solid-state electrolyte lithium secondary batteries were fabricated according to the above fabrication method using the ternary cathode materials obtained in examples 1-6 and comparative examples 1-3 as cathode materials to obtain examples 7-12 and comparative examples 4-6, with specific parameters as shown in table 3.
Rate performance test and cycle performance test were conducted on the solid electrolyte lithium secondary batteries obtained in examples 7 to 12 and comparative examples 10 to 18.
The all-solid-state lithium battery was placed at a constant temperature of 25 ℃, constant-current charging was performed at a current value of 0.05C (20h, 1C ═ 1mA calculated as a positive electrode) relative to the theoretical capacity of the all-solid-state lithium battery, and charging was terminated at a voltage of 4.2V. Then, the discharge was similarly performed at a current of 0.05C, and the discharge was terminated when the voltage was 3.0V. Thereby obtaining the coulombic efficiency and the discharge capacity of the battery as the result of the rate performance detection.
After 1000 charge and discharge cycles at 0.1C were performed from the second cycle, and after 1000 cycles were measured, the capacitance was measured and the capacitance retention rate was calculated as a cycle performance measurement result, which is shown in table 3.
Table 3.
Ternary positive electrode material First week discharge capacity mAh/g Capacity retention after 1000 charge-discharge cycles%
Example 7 Example 1 190 89
Example 8 Example 2 218 82
Example 9 Example 3 198 84
Example 10 Example 4 189 86
Example 11 Example 5 205 83
Example 12 Example 6 188 85
Comparative example 10 Comparative example 1 185 86
Comparative example 11 Comparative example 2 186 88
Comparative example 12 Comparative example 3 165 89
Comparative example 13 Comparative example 4 172 78
Comparative example 14 Comparative example 5 169 75
Comparative example 15 Comparative example 6 207 72
Comparative example 16 Comparative example 7 188 80
Comparative example 17 Comparative example 8 192 82
Comparative example 18 Comparative example 9 187 82
As can be seen by comparing the results in Table 3, the rate capability and cycle performance of examples 7-12 are both better than those of comparative examples 11-15, and comparative example 15 is found to have a lower cycle performance than comparative examples 11 and 14. When the ternary cathode material is used as a cathode in a solid lithium storage battery, the cycle performance, the rate capability and the safety performance of the solid lithium storage battery are improved.
Therefore, the ternary cathode material has a mixed core-shell structure in which particles of the ternary cathode material are formed by mixing inorganic solid electrolyte microcrystals and aluminum oxide to coat nickel-cobalt-manganese ternary cathode particles, the inorganic solid electrolyte microcrystals in the shell layer are embedded and fixed to form an ion conduction channel communicated with the outer side surface of the shell layer and the outer surface of the core, so that the lithium ion conductivity of the shell layer is improved, meanwhile, the solid electrolyte is mixed through the aluminum oxide and is compositely fixed to the surface of the core, and the interface separation of the ternary material and the solid electrolyte in the cathode caused by the volume change of the ternary material in the sufficient electrical process is reduced, so that the interface bonding performance inside the cathode is enhanced, and the ion conductivity of the cathode and the safety performance of the cathode are improved.
As can be seen by comparing the results in Table 3, the rate capability and cycle capability of example 7 are both superior to those of comparative examples 16-18. The ratio of the particle size of the inorganic solid electrolyte microcrystal to the shell thickness influences the formation distribution condition of the ion conduction channel, and the ratio of the particle size of the inorganic solid electrolyte microcrystal to the shell thickness in the ternary cathode material is preferably 0.65-1. Meanwhile, when the mass ratio of the inorganic solid electrolyte microcrystal to the aluminum oxide in the shell layer is 1-2, the structural strength of the shell layer can be enhanced, the limiting effect of the shell layer on the volume change of the core is further enhanced, and the contribution of the anode prepared from the ternary anode material in the improvement of the cycle performance of the lithium storage battery is further improved.
Solid-liquid mixed electrolyte lithium accumulator
A solid-liquid mixed electrolyte lithium storage battery comprises a positive plate, a negative plate, a mixed solid-liquid electrolyte membrane arranged between the positive plate and the negative plate, an outer packaging membrane, a positive terminal and a negative terminal.
The positive electrode sheet is the same as that in the above-described solid electrolyte lithium secondary battery. The negative electrode sheet is the same as that in the above solid electrolyte lithium secondary battery.
The mixed solid-liquid electrolyte membrane consists of an organic polymer base membrane, a solid electrolyte, an organic polymer interface modifier and a lithium salt, wherein the mass ratio of the solid electrolyte to the organic polymer interface modifier to the lithium salt is (50-90): (5-20): (0.1-5).
The organic polymer-based membrane has a thickness of 3 μm and is one of a PP separator, a PE separator, or a PP/PE composite separator, here a PP separator.
The solid electrolyte is one of sulfide-type solid electrolyte, oxide-type solid electrolyte, and polymer solid electrolyte, here is sulfide-type solid electrolyte membrane, and is Li2S-P2S5And (4) preparing the system.
The polymer additive is one or more of polyethylene oxide (PEO), polysiloxane, polypropylene carbonate (PPC), polyethylene carbonate (PEC), polytrimethylene carbonate (PTMC), Vinylene Carbonate (VC), fluoromethyl carbonate, fluoroethyl carbonate, here PEC.
The lithium salt is LiClO4、LiAsF6、LiBF4、LiPF6、LiCF3SO3、LiTFSI、LiC(CF3SO2)3LiBOB, here LiClO4、LiPF6The mixture is mixed according to the molar ratio of 1: 1.
The preparation method of the solid-liquid mixed electrolyte lithium storage battery comprises the following steps:
A. and mixing the positive electrode material, the conductive agent and the binder into slurry according to the mass ratio of 86:7:7, coating the slurry on an aluminum current collector with the thickness of 0.8 mu m, and drying to obtain the positive electrode plate.
B. The anode material, the solid electrolyte, the conductive agent and the binder are sequentially mixed according to the mass ratio of 85: 5: 5: 5, mixing into slurry, coating the slurry on a copper current collector with the diameter of 8 mu m, and drying to obtain the negative plate.
C. Mixing inorganic solid electrolyte, organic polymer interface modifier and lithium salt in proportion to prepare slurry, adding the uniformly mixed slurry into an extruder, heating and mixing by the extruder to obtain solid-liquid mixed electrolyte master batch, wherein the inorganic solid electrolyte in the solid-liquid mixed electrolyte master batch is LGAP.
D. And C, extruding the solid-liquid mixed electrolyte masterbatch prepared in the step C through an extruder, and uniformly coating the solid-liquid mixed electrolyte masterbatch on two sides of the organic polymer base film, wherein the coating thickness of the two sides is 8 micrometers, so as to obtain the mixed solid-liquid electrolyte film.
E. And D, molding the mixed solid-liquid electrolyte membrane obtained in the step D, the positive plate obtained in the step A and the negative plate obtained in the step B by a hot pressing method to prepare a composite battery cell structure with a multilayer structure of the solid-liquid electrolyte membrane, the positive plate, the solid-liquid electrolyte membrane and the negative plate, mounting a positive terminal and a negative terminal, and coating an aluminum plastic film to obtain the solid-liquid mixed electrolyte lithium storage battery.
Solid-state electrolyte lithium secondary batteries were fabricated using the ternary cathode materials obtained in examples 1-6 and comparative examples 1-3 according to the above fabrication method to obtain examples 13-18 and comparative examples 7-9, with specific parameters as shown in table 5.
Rate performance test and cycle performance test were conducted on the solid-liquid mixed electrolyte lithium secondary batteries of examples 13 to 18 and comparative examples 19 to 27, and the test results are shown in table 4.
TABLE 4
Figure BDA0002254696930000131
Figure BDA0002254696930000141
As can be seen by comparing the results in Table 4, the rate capability and cycle performance of examples 13-18 are both lower than those of comparative examples 19-24, and comparative example 19 is found to have lower cycle performance than comparative examples 22 and 24. When the ternary anode material is prepared into an anode in a lithium storage battery for use, the cycle performance, the rate capability and the safety performance of the solid-liquid mixed electrolyte lithium storage battery are improved.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (9)

1. The ternary positive electrode material is characterized by being composed of ternary positive electrode powder of a core-shell structure, wherein the ternary positive electrode powder comprises an inner core and a shell layer, the inner core is a nickel-cobalt-manganese ternary material, the shell layer comprises aluminum oxide and inorganic solid electrolyte microcrystals which are mixed, the inorganic solid electrolyte microcrystals are inorganic oxide solid electrolytes or fast ion conductor solid electrolytes, the inorganic solid electrolyte microcrystals are embedded and fixed in the aluminum oxide in the shell layer, ion conduction channels are constructed by the inorganic solid electrolyte microcrystals alone or in combination, and the ion conduction channels are communicated with the outer surface of the shell layer and the outer surface of the inner core.
2. The ternary positive electrode material for a long-cycle-life lithium secondary battery as claimed in claim 1, wherein the diameter of the core is 3 to 10 μm, and the thickness of the shell is 0.2 to 1 μm.
3. The ternary positive electrode material for a long-cycle-life lithium secondary battery as claimed in claim 2, wherein the ratio of the particle size of the inorganic solid electrolyte crystallite to the shell thickness is 0.65 to 1.
4. The ternary cathode material for a long-cycle-life lithium secondary battery as claimed in claim 1, wherein the mass ratio of inorganic solid electrolyte crystallites to alumina in the shell layer is 1 to 2.
5. The ternary positive electrode material for a long-cycle-life lithium secondary battery according to claim 1, wherein the inorganic solid electrolyte crystallites are Li1+xAlxGe2-x(PO4)3(LAGP)、Li1+xAlxTi2-x(PO4)3(LATP) (x is more than 0 and less than or equal to 0.5).
6. The ternary positive electrode material for a long-cycle-life lithium secondary battery as claimed in claim 1, wherein the core is a nickel-cobalt-manganese ternary single crystal material.
7. The method for preparing a ternary positive electrode material for a long-cycle-life lithium secondary battery according to any one of claims 1 to 6, comprising the steps of,
s1: ball-milling the nickel-cobalt-manganese ternary material by using a ball mill until the particle size reaches 3-10 mu m to obtain nickel-cobalt-manganese ternary material powder;
s2: ball-milling the inorganic solid electrolyte by a ball mill until the particle size reaches less than 1 mu m to obtain inorganic solid electrolyte microcrystal;
s3: mixing an aluminum oxide precursor and water to prepare an aluminum oxide precursor solution, wherein the aluminum oxide precursor is one or more of aluminum acetate, aluminum nitrate and aluminum sulfate, and the concentration of aluminum element in the aluminum oxide precursor solution is 3-10 wt%;
s4: adding the nickel-cobalt-manganese ternary material powder prepared by the step S1 and the inorganic solid electrolyte microcrystal prepared by the step S2 into the alumina precursor solution prepared by the step S3, and then adding citric acid and glycol to form a mixed suspension, wherein the mass fractions of the citric acid and the glycol in the suspension are both 0.5-1 wt%; adding ammonia water into the suspension, adjusting the pH value to 9-10, heating and stirring at 80 ℃ after dropwise adding is completed until precursor gel is formed, wherein the mass parts of the nickel-cobalt-manganese ternary material in the precursor gel are 70-94, the mass parts of the inorganic solid electrolyte microcrystal are 3-20, and the mass parts of the aluminum oxide obtained by equivalent conversion of aluminum hydroxide are 3-10;
s5: and sintering the precursor gel prepared in the step S4 at 150-200 ℃ for 2h in an air atmosphere, and then sintering at 500-700 ℃ for 4h in a nitrogen atmosphere to obtain the ternary cathode material for the lithium storage battery with long cycle life.
8. Use of a ternary positive electrode material for long cycle life lithium batteries according to any one of claims 1 to 6 in solid state lithium batteries.
9. Use of the ternary positive electrode material for long cycle life lithium secondary batteries according to any one of claims 1 to 6 in solid-liquid hybrid lithium secondary batteries.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113451566A (en) * 2021-06-22 2021-09-28 合肥国轩高科动力能源有限公司 Composite coated positive electrode material and preparation method and application thereof
CN114709412A (en) * 2022-04-25 2022-07-05 浙江锋锂新能源科技有限公司 High-temperature-resistant positive electrode material, electrolyte composition, lithium battery and preparation method
CN114784235A (en) * 2022-03-29 2022-07-22 万向一二三股份公司 High-voltage composite positive plate, preparation method thereof and all-solid-state lithium battery

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103636660A (en) * 2013-11-26 2014-03-19 肇庆市真格生物科技有限公司 Environmental-friendly particulate agent for controlling sugarcane pests
CN105244488A (en) * 2015-11-16 2016-01-13 湖南杉杉能源科技股份有限公司 Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material
JP2017130471A (en) * 2017-04-28 2017-07-27 株式会社サムスン日本研究所 All-solid-state lithium ion secondary battery and method of manufacturing all-solid-state lithium ion secondary battery
US20170338522A1 (en) * 2014-10-28 2017-11-23 University Of Maryland, College Park Interfacial layers for solid-state batteries and methods of making same
US9966644B2 (en) * 2014-09-15 2018-05-08 Samsung Electronics Co., Ltd. Cathode, lithium air battery including the same, and method of preparing the cathode
CN108206277A (en) * 2016-12-20 2018-06-26 宁德时代新能源科技股份有限公司 Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery
CN108598400A (en) * 2018-04-11 2018-09-28 桑德集团有限公司 A kind of three-layer nuclear shell structure positive electrode, preparation method and lithium ion battery
CN109273678A (en) * 2018-08-17 2019-01-25 北京工业大学 A kind of regeneration anode material for lithium-ion batteries and preparation method thereof
CN109698334A (en) * 2018-12-18 2019-04-30 桑顿新能源科技有限公司 Positive plate, lithium titanate battery and preparation method thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103636660A (en) * 2013-11-26 2014-03-19 肇庆市真格生物科技有限公司 Environmental-friendly particulate agent for controlling sugarcane pests
US9966644B2 (en) * 2014-09-15 2018-05-08 Samsung Electronics Co., Ltd. Cathode, lithium air battery including the same, and method of preparing the cathode
US20170338522A1 (en) * 2014-10-28 2017-11-23 University Of Maryland, College Park Interfacial layers for solid-state batteries and methods of making same
CN105244488A (en) * 2015-11-16 2016-01-13 湖南杉杉能源科技股份有限公司 Compound cladding positive pole material of lithium ion battery and preparation method of compound cladding positive pole material
CN108206277A (en) * 2016-12-20 2018-06-26 宁德时代新能源科技股份有限公司 Modified high-nickel ternary cathode material, preparation method thereof and lithium ion battery
JP2017130471A (en) * 2017-04-28 2017-07-27 株式会社サムスン日本研究所 All-solid-state lithium ion secondary battery and method of manufacturing all-solid-state lithium ion secondary battery
CN108598400A (en) * 2018-04-11 2018-09-28 桑德集团有限公司 A kind of three-layer nuclear shell structure positive electrode, preparation method and lithium ion battery
CN109273678A (en) * 2018-08-17 2019-01-25 北京工业大学 A kind of regeneration anode material for lithium-ion batteries and preparation method thereof
CN109698334A (en) * 2018-12-18 2019-04-30 桑顿新能源科技有限公司 Positive plate, lithium titanate battery and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
S. VERDIER 等: "XPS Study on Al2O3- and AlPO4-Coated LiCoO2 Cathode Material for High-Capacity Li Ion Batteries", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 *
李伟伟: "锂离子电池镍基正极材料水溶液体系中氧化铝包覆研究", 《电子元件与材料》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113451566A (en) * 2021-06-22 2021-09-28 合肥国轩高科动力能源有限公司 Composite coated positive electrode material and preparation method and application thereof
CN114784235A (en) * 2022-03-29 2022-07-22 万向一二三股份公司 High-voltage composite positive plate, preparation method thereof and all-solid-state lithium battery
CN114784235B (en) * 2022-03-29 2024-02-02 万向一二三股份公司 High-voltage composite positive plate, preparation method thereof and all-solid-state lithium battery
CN114709412A (en) * 2022-04-25 2022-07-05 浙江锋锂新能源科技有限公司 High-temperature-resistant positive electrode material, electrolyte composition, lithium battery and preparation method

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