CN112490415A - Lithium ion anode material lithium supplement additive and preparation method thereof - Google Patents

Lithium ion anode material lithium supplement additive and preparation method thereof Download PDF

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CN112490415A
CN112490415A CN201910865264.6A CN201910865264A CN112490415A CN 112490415 A CN112490415 A CN 112490415A CN 201910865264 A CN201910865264 A CN 201910865264A CN 112490415 A CN112490415 A CN 112490415A
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carbon
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lithium
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CN112490415B (en
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李哲
刘仲书
苏松
别晓非
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BASF Shanshan Battery Materials Co Ltd
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Hunan Shanshan Energy Technology Co Ltd
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Abstract

The invention discloses a lithium ion anode material lithium supplement additive, which comprises Li5FeO4Matrix and Li site5FeO4A coating layer on the surface of the substrate; the cladding layer includes Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating transition metal oxide layer on the surface of the first coating. The invention also discloses a preparation method of the lithium supplement additive, which comprises the following steps: firstly, preparing iron oxide coated by a carbon layer,then mixing by a wet method to prepare Li with carbon-coated surface5FeO4And finally mixing the lithium ion source with a transition metal ion salt solution and an ammonium hydroxide solution, and sintering at high temperature to obtain the lithium supplement additive. Double-layered coated Li of the invention5FeO4Lithium supplementing additive, Li5FeO4The matrix is micron-sized or nano-sized particles, the particles are uniform and controllable, the migration path of electrons and ions is shortened, and Li can be realized5FeO4The performance of lithium supplement performance of the material is exerted, and the service life of the lithium ion battery is prolonged.

Description

Lithium ion anode material lithium supplement additive and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a high-stability lithium ion positive electrode material lithium supplement additive and a preparation method thereof.
Background
During the first cycle of charging of the lithium ion battery, a solid electrolyte film (SEI film) is formed on the surface of the negative electrode, which consumes active lithium in the positive electrode, resulting in the first specific Capacity Loss (ICL) of the lithium ion battery. The irreversible capacity loss of the graphite cathode which is most widely used at present can reach 10 percent, and the irreversible capacity loss of silicon-based and tin-based cathodes with high specific capacity is even more than 30 percent, thereby greatly reducing the energy density of the lithium ion battery. Therefore, irreversible capacity loss of the lithium ion battery is usually compensated by a method of lithium supplement, the capacity of the positive electrode is restored, and lithium supplement is expected to be commercially applied in a short period of time.
Currently, lithium supplement methods are divided into positive electrode lithium supplement and negative electrode lithium supplement. The lithium supplement of the negative electrode is the most commonly used method, such as lithium powder supplement and lithium foil supplement, but because the lithium metal is a high-reactivity alkali metal, the lithium metal can react with water violently, the requirement on the environment is very high, and thus, the two negative electrode lithium supplement processes need to invest a large amount of funds to transform a production line and lithium supplement equipment. In the typical positive electrode lithium supplement process, a small amount of high-capacity lithium supplement additive is added in the positive electrode homogenizing process, and redundant Li elements are extracted from the high-capacity positive electrode materials and are inserted into a negative electrode to supplement irreversible capacity of initial charging and discharging in the charging process. The most common positive electrode lithium supplement additive at present is Li2NiO2、Li5FeO4、Li2MnO3、Li6CoO4、Li6MnO4、Li5ReO6Nanocomposites of Co and lithium salts (e.g. Li)2S/Co, LiF/Co and Li2O/Co), etc., wherein Li5FeO4Is a very ideal lithium ion anode material lithium supplement additive, and theoretically has every mol of Li5FeO45 Li can be provided+The specific capacity can reach 867mAh/g, and a certain amount of Li is mixed into the traditional anode material5FeO4The first efficiency and the energy density of the lithium ion battery can be obviously improved. However, Li5FeO4The material readily reacts chemically with carbon dioxide and water in the air, forming lithium carbonate and carbon dioxide on the surface, since Li5FeO4Active O on the surface of the particles2-Is easy to react with CO in the air2And H2Reaction of O to form CO3 2-And OH-And lithium ions are derived from Li5FeO4The interior of the particles migrate to the surface and form Li on the surface of the material2CO3And LiOH, the surface specifically having the following reaction: 2Li + CO3 2-/2OH-→Li2CO32LiOH, therefore, Li5FeO4It is highly susceptible to deterioration in air and the surface alkali residue of the material is too high, which affects the coating of the material, especially the formation of jelly-like shape during the homogenization process, mainly due to the fact that the surface alkali oxide content is too high to absorb water, if Li is used5FeO4Is doped into other anode materials as an anode lithium supplement agent (LiCoO)2，LiMn2O4NMC, NCA), etc., the surface alkaline compound affects the overall electrochemical performance of the battery, for example, increases irreversible capacity loss, deteriorates cycle performance. At present, the method is only limited to laboratory research, and industrial production is difficult to realize. Furthermore, Li5FeO4The conductivity of the material is very low, only 10-9Of the order of S/cm, is almost an insulator compound, resulting in Li5FeO4The total conductivity of the composite is extremely poor, and the specific capacity and the rate capability can not be exerted. Therefore, how to increase Li5FeO4The chemical stability and conductivity of materials in air environments are the focus of current technical research.
Patent No. CN108878849A mentions that Li source with core-shell structure is synthesized by dissolving lithium source, iron source and organic carbon source in proper molar ratio in water to prepare gel, then spray-drying to obtain precursor powder, calcining at high temperature for a period of time in inert gas atmosphere5FeO4C; albeit in Li5FeO4The material adopts surface coating, and Li can be coated to a certain extent5FeO4The coating/C can effectively isolate water and carbon dioxide in the air, but due to the limitation of the preparation method, the distribution and the coating thickness of the coating elements are difficult to control uniformly, particularly, the coating layer is easy to fall off due to the non-uniform coating, the coating effect is greatly reduced, and the water and the carbon dioxide in the air are difficult to effectively block Li5FeO4Erosion of the material.
Patent No. CN109428067A mentions in Li5FeO4Surface double-layer coating of carbon and Mo2C, however, realization of Mo2C coating, wherein the carbon source mainly adopts sucrose, glucose, fructose, epoxy resin and the like, and inert gas is usually mixed with hydrogen, so that the Mo reduction effect is improved, and the coating process is complex; mo2Coating Li with C as main material5FeO4Can isolate water in air from Li5FeO4The material is corroded, but the cladding is still the combination of two substances, solid solution is not formed, and the effect of isolating corrosion is limited; at the same time, Mo is synthesized in the present stage2C needs to be carried out at a higher temperature, the reaction needs to be carried out at 700-900 ℃, and incomplete carbonization can be caused when the reaction temperature is lower. Higher synthesis temperature can inevitably cause Mo2C is sintered and agglomerated, and incomplete reaction can be caused when the temperature is low, so that the coating effect can be influenced to a certain degree; therefore, there is a need for a lithium supplement additive and a method for preparing the same, which can be controlled to prepare Li with a smooth film layer and uniform coating thickness and composition5FeO4A material.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and provides a lithium ion cathode material lithium supplement additive and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a lithium ion anode material lithium supplement additive comprises Li5FeO4Matrix and coating Li5FeO4A coating layer on the surface of the substrate; the coating layer includes Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating transition metal oxide layer on the surface of the first coating.
In the lithium supplement additive, the transition metal oxide is preferably selected from oxides of one or more elements of Ti, Al, Zn, Cr, V, Zr and Mg.
In the lithium supplement additive, the first coating carbon layer preferably has a mass of Li5FeO41-5 wt% of the matrix mass; the second cladding layer transition metal oxide layer is opposite to Li5FeO41-10 wt% of the matrix mass.
As a general inventive concept, the present invention also provides a method for preparing the lithium supplement additive, comprising the steps of:
(1) adding iron oxide into an organic carbon source homogeneous dispersion liquid, uniformly stirring and dispersing to coat a layer of carbon source solution on the surface of the iron oxide, and carrying out heat treatment to crack the carbon source solution on the surface of the iron oxide particles into a simple substance carbon to obtain iron oxide coated by a carbon layer;
(2) carrying out wet mixing and spray drying on the iron oxide coated with the carbon layer obtained in the step (1) and a lithium source to obtain a powdery mixture, then carrying out high-temperature sintering under the protection of inert gas, and naturally cooling to room temperature along with a furnace to obtain Li coated with carbon on the surface5FeO4；
(3) Surface carbon-coated Li5FeO4Adding into a salt solution containing transition metal ions, adding ammonium hydroxide solution, stirring, and adding Li5FeO4Forming a uniform transition metal hydroxide precipitate layer on the surface of the carbon layer in situ, then sintering at high temperature under the protection of inert gas, and naturally cooling to room temperature along with the furnaceTo obtain carbon and transition metal oxide layer double-layer coated Li5FeO4Namely the lithium supplement additive.
In the preparation method, preferably, in the step (1), the organic carbon source homogeneous dispersion liquid is obtained by mixing an organic carbon source, a surfactant and an ethanol solvent, and performing ultrasonic dispersion uniformly; the organic carbon source is one or more of glucose, fructose, sucrose, soluble starch, succinic acid, citric acid, lactic acid and acetic acid; the surfactant is one or more of oleic acid, tetracosanoic acid, perfluorocarboxylic acid, silicone oil, polyether, triethylhexyl phosphoric acid and fatty acid. Further preferably, the ultrasonic dispersion time is 1 to 3 hours.
Further preferably, the molar ratio of the organic carbon source, the surfactant and the ethanol is (1-2): (8-12): (34-42).
In the above preparation method, preferably, in the step (1), the iron oxide is obtained by the following preparation method: adding a ferric iron salt solution into an ammonium hydroxide solution, stirring and dispersing, then carrying out ultrasonic treatment, standing, and then washing and heating the obtained precipitate to obtain reddish brown iron oxide; wherein the ferric salt solution is one or more of ferric nitrate solution, ferric sulfate solution, ferric chloride solution and ferric bromide solution, and the concentration of the solution is 0.5-4 mol g-1(ii) a The molar ratio of the trivalent ferric salt solution to the ammonium hydroxide solution is 1: 1-1: 3; the stirring speed is 100-500rpm, the stirring time is 20-60 minutes, the ultrasonic treatment frequency is 20-30Hz, and the treatment time is 10-30 minutes.
In the preparation method, the weight ratio of the organic carbon source to the iron oxide is preferably 1: 20-1: 10.
In the preparation method, preferably, in the step (1), the stirring speed is 200-800rpm, and the stirring time is 20-50 minutes; the heat treatment is to heat the mixture to 300-700 ℃ at a heating rate of 1-5 ℃/min and to sinter the mixture for 0.5-3 hours.
In the preparation method, preferably, in the step (2), the molar ratio of the lithium source to the iron oxide is (9-11): 1; during spray drying, the temperature of an air inlet is 150-200 ℃, the temperature of an air outlet is 100-150 ℃, and the feeding speed is 5-20 mL/min; the high-temperature sintering is that the temperature rise rate is increased to 650-900 ℃ at 1-10 ℃/min, and the temperature is kept for 3-10 h.
Preferably, in the preparation method, in the step (3), the high-temperature sintering refers to heating to 700-800 ℃ at a heating rate of 1-5 ℃/min and sintering for 5-10 hours; the molar ratio of the ammonium hydroxide solution to the transition metal ion salt is (1:1) - (3: 1); metal ions in solution of transition metal ion salt and Li of the surface-coated carbon layer5FeO4The molar ratio of (1: 10) to (1: 40).
In the preparation method, preferably, the inert gas is one or more of nitrogen, helium, neon, argon, krypton and xenon, and the gas flow is 3-8 m3/h。
In the preparation method, amorphous carbon is firstly used for coating iron oxide, and then a lithium source is added to form Li5FeO4The amorphous carbon can effectively inhibit high-temperature Li treatment in the process of the matrix5FeO4The crystal growth and particle agglomeration in the material synthesis process are favorable for Li5FeO4The material forms micron or nanometer particles with uniform and controllable particles, shortens the migration path of electrons and ions, improves the electrochemical performance and the anode lithium supplement performance, and can improve the carbon coating and Li5FeO4The degree of binding of; carbon-coated Li5FeO4Adding the particles to a solution of a transition metal ion salt, and adding to the solution an ammonium hydroxide solution which reacts with the compound containing the transition metal ion to form a transition metal oxide precipitate, thereby precipitating Li5FeO4In-situ reacting on the surface of carbon layer of the particle to generate a uniform and continuous transition metal hydroxide precipitate layer, and then performing heat treatment under the protection of inert atmosphere to obtain the Li-doped transition metal oxide5FeO4The surface of the material realizes double-layer coating of carbon coating and transition metal oxide coating. In the synthesis process, carbon and transition metal oxide are added in two times, the organic carbon source can generate gas in the cracking decomposition process, a large number of holes can be formed on the surface of the material, and the specific surface area of the material is increased; in addition, in situ generated carbon can inhibitThe growth of the particles effectively prevents the occurrence of particle agglomeration, and in Li5FeO4The uniform and compact coating layer is coated on the surface of the particle, so that not only can the tap density and the specific energy of the material be improved to a certain degree, but also a conductive network can be formed by the coating layer, the conductivity of the material can be obviously improved, and the electrochemical performance and the lithium supplement performance of the anode are improved; in addition, in Li5FeO4The surface is coated with a layer of transition metal oxide, and stable Li is uniformly formed on the surface5Fe1-xMxO4The (M is transition metal) solid solution interface reduces the direct contact of the material and the outside air, and effectively isolates moisture and carbon dioxide. The invention has the advantages of lower reaction temperature, simple process and good product stability.
Compared with the traditional method of directly applying Li5FeO4The surface is coated with carbon and metal elements by a dry method, and firstly Fe2O3Coating a layer of carbon and then coating by a wet method to obtain Li5FeO4the/C/metal oxide composite material has the advantages of uniform distribution of carbon and metal elements, good product consistency, compact coating layer and difficult shedding.
Compared with the prior art, the invention has the advantages that:
(1) the invention prepares the double-layer coating Li of the carbon layer and the transition metal oxide layer by sintering with a high-temperature solid-phase method5FeO4The positive electrode material lithium supplement additive: the organic carbon source is processed at high temperature under the oxygen-deficient condition to form amorphous carbon with a network shape, in Li5FeO4The amorphous carbon coating layer is formed on the surface, the combination is tight, the coating thickness is uniform, the coating is smooth and not easy to fall off, the defect that the direct coating thickness is difficult to control in the prior art is overcome, an integral conductive network can be formed, and the Li can be obviously improved5FeO4Electron conductivity of (2); then Li is coated by a wet method5FeO4Can improve carbon coating and Li5FeO4While the amorphous carbon is effective in inhibiting high temperature processing of Li when iron oxide reacts with lithium source5FeO4Crystal growth and particle agglomeration are inhibited in the material synthesis process, and Li is favorably adopted5FeO4The material forms micron or nanometer particles with uniform and controllable particles, shortens the migration path of electrons and ions, and improves the electrochemical performance and the lithium supplement performance of the anode; particularly when the electrode is applied to a battery, the volume expansion of the electrode can be effectively relieved; then Li5FeO4The surface of the carbon layer is coated with a layer of transition metal oxide, and stable Li is uniformly formed on the surface of the carbon layer5Fe1-xMxO4(M is a transition metal) solid solution interface, thereby effectively reducing Li in the interior5FeO4The contact area of the particles and the outside air effectively inhibits Li5FeO4The reactivity of the material with carbon dioxide and water improves Li5FeO4Chemical stability of the material.
(2) The carbon layer and transition metal oxide layer of the present invention are double-coated with Li5FeO4In the lithium-supplementing additive for the positive electrode material of (1), Li5FeO4The matrix is micron or nano-scale particles, the particles are uniform and controllable, the migration path of electrons and ions is shortened, and the rapid electron and lithium ion channels ensure Li of the inner layer5FeO4Sufficient lithium ion exchange with active material is performed, thereby more effectively realizing Li5FeO4The performance of lithium supplement performance of the material is exerted, and the service life of the lithium ion battery is prolonged.
(3) The transition metal oxide coating of the present invention is on Li5FeO4The surface of the carbon layer of (2) is uniformly formed with stable Li5Fe1-xMxO4(M is transition metal) solid solution interface, can effectively inhibit electrolyte from reacting with Li5FeO4Erosion of (2); the transition metal oxide coating layer forms Li-M-O phase in the charge-discharge process, and increases material Li+Ionic conductivity, promotes Li5FeO4Electrochemical properties of the material.
(4) The preparation method disclosed by the invention has the characteristics of simple and easily-controlled process, good repeatability, environmental friendliness, uniform coating, low cost and high efficiency, and has a wide industrial application prospect.
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 introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows Li obtained in example 1 of the present invention5FeO4XRD lines after exposure to air for different times;
fig. 2 is a graph comparing the first charge and discharge curves of the sample S10 assembled lithium battery and the sample S11 assembled lithium battery of example 1 according to the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the lithium ion anode material lithium supplement additive comprises Li5FeO4Matrix, located in Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating alumina layer on the surface of the first coating; wherein the mass of the carbon layer is Li5FeO42.3 wt% of the mass of the matrix; aluminum oxide layer relative to Li5FeO43.3 wt% of the mass of the matrix.
The preparation method of the lithium supplement additive for the lithium ion cathode material comprises the following steps:
(1) preparing a carbon-coated iron oxide material:
1.1) 100mL of the solution was added at a concentration of 0.5 mol. L-1Adding the ferric sulfate solution into an ammonium hydroxide solution with the concentration of 2 mol.L < -1 >, magnetically stirring and dispersing for 30 minutes (the stirring speed is 450rpm/min), ultrasonically treating for 20 minutes, standing until the reddish brown precipitate is completely precipitated, recovering the supernatant, then washing the precipitate twice, drying at 60 ℃, transferring into a tubular furnace with argon flow, heating to 400 ℃ at the heating speed of 3 ℃/min, sintering at the high temperature for 8 hours, and naturally cooling to room temperature to obtain reddish brown ferric oxide;
1.2) mixing glucose with oleic acid and ethanol solvent according to the molar ratio of 1:10:36, and carrying out ultrasonic treatment for 2 hours to obtain a glucose homogeneous solution;
1.3) mixing the glucose homogeneous solution prepared in the step 1.2) with the iron oxide prepared in the step 1.1) according to a molar ratio of 1:10, stirring at a high speed (the stirring speed is 600rpm/min) for dispersing for 30 minutes, coating a layer of carbon source solution on the surface of the iron oxide under the action of a surfactant, heating to 600 ℃ at a heating speed of 3 ℃/min, and sintering at a high temperature for 10 hours to crack the carbon source solution into a carbon simple substance on the surface of iron oxide particles, namely forming a layer of carbon layer on the surface of the iron oxide;
(2) carbon-coated Li5FeO4The preparation of (1):
2.1) according to Li: fe-5: 1, mixing the synthesized carbon-coated iron oxide and lithium hydroxide, adding 100mL of alcohol, putting the mixture into a nylon tank, ball-milling and mixing the mixture on a ball mill for 3 hours, and performing spray drying (the temperature of an air inlet of a spray dryer is 150 ℃, the temperature of an air outlet of the spray dryer is 100 ℃, and the feeding speed is 10mL/min) to obtain a powdery mixture;
2.2) placing the mixture obtained in step 2.1) into a tube furnace at 6m3Heating to 850 ℃ at the speed of 5 ℃/min under the argon atmosphere, sintering for 15 hours, and naturally cooling to room temperature along with the furnace to obtain Li with the surface coated with the carbon layer5FeO4；
(3) Carbon and alumina double-layer coated Li5FeO4Preparation:
3.1) coating the surface with Li of the carbon layer5FeO4Adding into aluminum sulfate solution with concentration of 1mol/L according to aluminum ions and Li in the surface coating carbon layer5FeO4The molar ratio of the components is 1:10 to prepare a mixture;
3.2) the concentration is 0.5 mol.L-1Ammonium hydroxide solution was slowly added to the mixture and stirred until the solution was pasty, thereby dissolving in Li5FeO4A uniform aluminum hydroxide precipitation layer is formed on the surface of the carbon layer in situ;
3.3) placing the material obtained in step 3.2) into a tube furnace at 3m3Heating to 700 ℃ at the speed of 3 ℃/min under the argon atmosphere with the flow of/h, sintering for 6 hours, and then naturally cooling to room temperature along with the furnace to obtain the carbon and aluminum oxide double-layer coated Li5FeO4The composite, i.e., lithium ion positive electrode material lithium supplement additive, is labeled S10.
Samples of S10 were exposed to air for 1 day, 2 days, 3 days, respectively, and the resulting samples were labeled S41, S42, and S43, respectively.
Example 2:
the lithium ion anode material lithium supplement additive comprises Li5FeO4Matrix, located in Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating titanium oxide layer on the surface of the first coating; wherein the mass of the carbon layer is Li5FeO44.7 wt% of the mass of the matrix; titanium oxide layer with respect to Li5FeO45.2 wt% of the mass of the matrix.
The preparation method of the lithium supplement additive for the lithium ion cathode material comprises the following steps:
(1) preparing a carbon-coated iron oxide material:
1.1) 100mL of the solution was added at a concentration of 0.5 mol. L-1Adding ferric chloride solution with the concentration of 3 mol.L-1Magnetically stirring and dispersing in ammonium hydroxide solution for 40 min (stirring speed of 400rpm/min), ultrasonic treating for 15min, standing until the reddish brown precipitate is completely removed, recovering supernatant, washing the precipitate twice, drying at 60 deg.C,transferring into a tubular furnace filled with argon flow, heating to 400 ℃ at the heating rate of 3 ℃/min, sintering at the temperature for 8 hours at high temperature, and naturally cooling to room temperature to obtain reddish brown iron oxide;
1.2) mixing sucrose, tetracosanoic acid and an ethanol solvent according to a molar ratio of 1:10:34, and carrying out ultrasonic treatment for 2 hours to obtain a sucrose homogeneous solution;
1.3) mixing the sucrose homogeneous solution with the prepared iron oxide according to the molar ratio of 1:10, stirring at a high speed (the stirring speed is 550rpm/min), dispersing for 50 minutes, coating a layer of carbon source solution on the surface of the iron oxide under the action of a surfactant, heating to 600 ℃ at the heating speed of 3 ℃/min, and sintering at the high temperature for 10 hours to crack the carbon source solution into a carbon simple substance on the surface of the iron oxide particles, namely forming a carbon film layer on the surface of the iron oxide;
(2) carbon-coated Li5FeO4The preparation of (1):
2.1) according to Li: fe ═ 5.5: 1, mixing the synthesized iron oxide coated by the carbon film with lithium nitrate, adding 200mL of deionized water, putting the mixture into a nylon tank, mixing the mixture on a ball mill for 4 hours, and performing spray drying (the temperature of an air inlet of a spray dryer is 120 ℃, the temperature of an air outlet of the spray dryer is 150 ℃, and the feeding speed is 6mL/min) to obtain a powdery mixture;
2.2) placing the mixture obtained in step 2.1) into a tube furnace at 6m3Heating to 800 ℃ at the speed of 5 ℃/min under the argon atmosphere, sintering for 20 hours, and then naturally cooling to room temperature along with the furnace to obtain the Li with carbon-coated surface5FeO4。
(3) Carbon and titanium oxide surface double-layer coated Li5FeO4Preparation:
3.1) carbon-coated Li5FeO4Adding into 1mol/L titanium chloride solution, according to the titanium ion and Li coated with carbon on the surface5FeO4In a molar ratio of 1:10 to form a mixture;
3.2) the concentration is 2 mol. L-1Ammonium hydroxide solution is slowly added to the mixture and stirred until the solution is pastyIn the presence of Li5FeO4Forming a uniform titanium hydroxide precipitate layer on the surface of the carbon layer in situ;
3.3) placing the material obtained in 3.2) in a tube furnace at 5m3Heating to 750 ℃ at the speed of 3 ℃/min under the nitrogen flow, sintering for 5 hours, and then naturally cooling to room temperature along with the furnace to obtain the carbon and titanium oxide double-layer coated Li5FeO4Composite material, labeled S20.
The S20 samples were exposed to air for 3 days and the resulting samples were individually labeled S23.
Example 3:
the lithium ion anode material lithium supplement additive comprises Li5FeO4Matrix, located in Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating zirconia layer on the surface of the first coating; wherein the mass of the carbon layer is Li5FeO41.2 wt% of the mass of the matrix; zirconium oxide with respect to Li5FeO45.3 wt% of the mass of the matrix.
The preparation method of the lithium supplement additive for the lithium ion cathode material comprises the following steps:
(1) preparing a carbon-coated iron oxide material:
1.1) 150mL of 1 mol. L-1Adding the ferric nitrate solution to the solution with the concentration of 2 mol.L-1Magnetically stirring and dispersing in an ammonium hydroxide solution for 30 minutes (the stirring speed is 400rpm/min), ultrasonically treating for 20 minutes, standing until the reddish brown precipitate is completely, recovering the supernatant, washing the precipitate twice, drying at 60 ℃, transferring into a tubular furnace filled with argon flow, heating to 500 ℃ at the heating speed of 3 ℃/min, sintering at the high temperature for 6 hours, and naturally cooling to room temperature to obtain reddish brown iron oxide;
1.2) mixing lactic acid, perfluorocarboxylic acid and an ethanol solvent according to a molar ratio of 1:10:34, and performing ultrasonic treatment for 2 hours to obtain a lactic acid homogeneous solution;
1.3) mixing the lactic acid homogeneous solution with the iron oxide obtained in the step 1.1) according to a molar ratio of 1:10, stirring at a high speed (the stirring speed is 500rpm/min) for dispersing for 60 minutes, coating a layer of carbon source solution on the surface of the iron oxide under the action of a surfactant, heating to 500 ℃ at a heating speed of 3 ℃/min, and sintering at a high temperature for 12 hours to crack the carbon source solution into a carbon simple substance on the surface of iron oxide particles, namely forming a layer of carbon layer on the surface of the iron oxide;
(2) carbon-coated Li5FeO4The preparation of (1):
2.1) according to Li: fe is 6: 1, mixing iron oxide coated by the carbon layer and lithium oxide, adding 200mL of deionized water, putting the mixture into a nylon tank, mixing for 4 hours on a ball mill, and performing spray drying (the temperature of an air inlet of a spray dryer is 120 ℃, the temperature of an air outlet of the spray dryer is 150 ℃, and the feeding speed is 6mL/min) to obtain a powdery mixture;
2.2) placing the mixture obtained in 2.1) in a tube furnace at 6m3Heating to 900 ℃ at the speed of 5 ℃/min under the argon atmosphere, sintering for 15 hours, and then naturally cooling to room temperature along with the furnace to obtain the Li with carbon-coated surface5FeO4；
(3) Carbon and zirconium oxide double-layer coated Li5FeO4Preparation:
3.1) coating the surface with Li of the carbon layer5FeO4Adding the powder into a zirconium chloride solution with the concentration of 0.5mol/L according to the zirconium ions in the solution containing zirconium chloride and Li of the surface coating carbon layer5FeO4In a molar ratio of 1:15 to form a mixture;
3.2) the concentration is 3 mol. L-1Ammonium hydroxide solution is slowly added to the mixture and stirred until the solution is pasty, thereby dissolving in the Li5FeO4Forming a uniform titanium hydroxide precipitate layer on the surface of the carbon layer in situ;
3.3) placing the material obtained in 3.2) in a tube furnace at 5m3Heating to 700 ℃ at the speed of 3 ℃/min in nitrogen atmosphere, sintering for 8 hours, and naturally cooling to room temperature along with the furnace to obtain carbon and zirconium oxide double-layer coated Li5FeO4Composite material, labeled S30.
The S30 sample was exposed to air for 3 days and the resulting sample was labeled S313.
Example 4:
the lithium ion anode material lithium supplement additive comprises Li5FeO4Matrix, located in Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating zinc oxide layer on the surface of the first coating; wherein the mass of the carbon layer is Li5FeO41.6 wt% of the mass of the matrix; zinc oxide layer relative to Li5FeO42.1 wt% of the mass of the matrix.
The preparation method of the lithium supplement additive for the lithium ion cathode material comprises the following steps:
(1) preparing a carbon-coated iron oxide material:
1.1) 100mL of the solution was added at a concentration of 0.5 mol. L-1Adding the ferric sulfate solution to the solution with the concentration of 2 mol.L-1Magnetically stirring and dispersing in an ammonium hydroxide solution for 30 minutes (the stirring speed is 450rpm/min), performing ultrasonic treatment for 10 minutes, standing until a reddish brown precipitate is completely precipitated, recovering a supernatant, washing the precipitate twice, drying at 60 ℃, transferring into a tubular furnace filled with argon flow, heating to 400 ℃ at the heating speed of 3 ℃/min, sintering at high temperature for 8 hours, and naturally cooling to room temperature to obtain reddish brown iron oxide;
1.2) mixing soluble starch with fatty acid and ethanol solvent according to the molar ratio of 1:8:40, and carrying out ultrasonic treatment for 3 hours to obtain starch homogeneous liquid;
1.3) mixing the starch homogeneous solution with iron oxide according to the molar ratio of 1:15, stirring at a high speed (the stirring speed is 700rpm/min) for 20 minutes, coating a layer of carbon source solution on the surface of the iron oxide under the action of a surfactant, heating to 550 ℃ at the heating speed of 3 ℃/min, and sintering at a high temperature for 12 hours to ensure that the carbon source solution is cracked into a carbon simple substance on the surface of the iron oxide particles, namely a carbon layer is formed on the surface of the iron oxide;
(2) carbon-coated Li5FeO4The preparation of (1):
2.1) according to Li: fe ═ 5.5: 1, mixing iron oxide coated by the carbon layer and lithium oxalate, adding 200mL of deionized water, putting the mixture into a nylon tank, mixing for 4 hours on a ball mill, and performing spray drying (the temperature of an air inlet of a spray dryer is 150 ℃, the temperature of an air outlet of the spray dryer is 120 ℃, and the feeding speed is 5mL/min) to obtain a powdery mixture;
2.2) placing the mixture obtained in step 2.1) into a tube furnace at 6m3Heating to 750 ℃ at the speed of 5 ℃/min under the argon atmosphere, sintering for 25 hours, and then naturally cooling to room temperature along with the furnace to obtain the Li with carbon-coated surface5FeO4；
(3) Carbon and zinc oxide surface double-layer coated Li5FeO4Preparation:
3.1) coating the surface with Li of the carbon layer5FeO4Adding the powder into a zinc sulfate solution with the concentration of 1.5mol/L according to the zinc ions in the zinc sulfate solution and Li of the surface coating carbon layer5FeO4In a molar ratio of 1: 25 to form a mixture;
3.2) the concentration is 2 mol. L-1Ammonium hydroxide solution is slowly added to the mixture and stirred until the solution is pasty, thereby dissolving in the Li5FeO4Forming a uniform zinc hydroxide precipitate layer on the surface of the carbon layer in situ;
3.3) placing the material obtained in 3.2) in a tube furnace at 6m3Heating to 730 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, sintering for 8 hours, and then naturally cooling to room temperature along with the furnace to obtain the carbon and zinc oxide double-layer coated Li5FeO4Composite material, labeled S40.
The S40 samples were exposed to air for 3 days and the resulting samples were individually labeled S43.
Example 5:
the lithium ion anode material lithium supplement additive comprises Li5FeO4Matrix, located in Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating magnesium oxide layer on the surface of the first coating; wherein the mass of the carbon layer is Li5FeO41.2 wt% of the mass of the matrix; magnesium oxide layer relative to Li5FeO41.3 wt% of the mass of the matrix.
The preparation method of the lithium supplement additive for the lithium ion cathode material comprises the following steps:
(1) preparing a carbon-coated iron oxide material:
1.1) 100mL of the solution was added at a concentration of 0.5 mol. L-1Adding the ferric sulfate solution to the solution with the concentration of 2 mol.L-1Magnetically stirring and dispersing in an ammonium hydroxide solution for 30 minutes (the stirring speed is 450rpm/min), performing ultrasonic treatment for 10 minutes, standing until a reddish brown precipitate is completely precipitated, recovering a supernatant, washing the precipitate twice, drying at 60 ℃, transferring into a tubular furnace filled with argon flow, heating to 400 ℃ at the heating speed of 3 ℃/min, sintering at high temperature for 8 hours, and naturally cooling to room temperature to obtain reddish brown iron oxide;
1.2) mixing citric acid with silicone oil and ethanol solvent according to a molar ratio of 1:10:36, and performing ultrasonic treatment for 2 hours to uniformly disperse the mixture to obtain a citric acid homogeneous solution;
1.3) mixing the citric acid homogeneous solution with the iron oxide obtained in the step 1.1) according to a molar ratio of 1:20, stirring at a high speed (the stirring speed is 650rpm/min) for dispersing for 40 minutes, coating a layer of carbon source solution on the surface of the iron oxide under the action of a surfactant, heating to 500 ℃ at a heating speed of 3 ℃/min, sintering at a high temperature for 12 hours, and cracking the carbon source solution into a carbon simple substance on the surface of iron oxide particles to form a carbon film layer to cover the surface of the iron oxide;
(2) carbon-coated Li5FeO4The preparation of (1):
2.1) according to Li: fe-7: 1, mixing the synthesized carbon film layer coated iron oxide and lithium acetate, adding 150mL of acetone, putting the mixture into a nylon tank, mixing for 4 hours on a ball mill, and performing spray drying (the temperature of an air inlet of a spray dryer is 120 ℃, the temperature of an air outlet of the spray dryer is 120 ℃, and the feeding speed is 5mL/min) to obtain a powdery mixture;
2.2) placing the mixture obtained in step 2.1) into a tube furnace at 6m3Heating to 800 ℃ at the speed of 5 ℃/min under the argon atmosphere, sintering for 15 hours, and then naturally cooling to room temperature along with the furnace to obtain the Li with carbon-coated surface5FeO4；
(3) Carbon and magnesium oxide double-layer coated Li5FeO4Preparation:
3.1) coating the surface with Li of the carbon layer5FeO4Adding the powder into a magnesium chloride solution with the concentration of 1.0mol/L according to the magnesium ions in the magnesium chloride solution and Li of the surface coating carbon layer5FeO4In a molar ratio of 1:20 to form a mixture;
3.2) mixing 3.0 mol. L-1Ammonium hydroxide solution is slowly added to the mixture and stirred until the solution is pasty, thereby dissolving in the Li5FeO4Forming a uniform magnesium hydroxide precipitate layer on the surface of the carbon layer in situ;
3.3) placing the material obtained in 3.2) in a tube furnace at 6m3Heating to 710 ℃ at the speed of 3 ℃/min under the nitrogen atmosphere, sintering for 10 hours, and then naturally cooling to room temperature along with the furnace to obtain the carbon and magnesium oxide double-layer coated Li5FeO4Composite material, labeled S50.
The S50 sample was exposed to air for 3 days and the resulting sample was labeled S53.
Example 6:
the lithium ion anode material lithium supplement additive comprises Li5FeO4Matrix, located in Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating chromium oxide layer on the surface of the first coating; wherein the mass of the carbon layer is Li5FeO41.0 wt% of the mass of the matrix; chromium oxide relative to Li5FeO42.0 wt% of the mass of the matrix.
The preparation method of the lithium supplement additive for the lithium ion cathode material comprises the following steps:
(1) preparing a carbon-coated iron oxide material:
1.1) adding 150mL of 1 mol.L < -1 > ferric nitrate solution into 2 mol.L < -1 > ammonium hydroxide solution, magnetically stirring and dispersing for 30 minutes (the stirring speed is 400rpm/min), carrying out ultrasonic treatment for 20 minutes, standing until the reddish brown precipitate is completely, recovering the supernatant, then washing the precipitate twice, drying at 60 ℃, transferring the precipitate into a tubular furnace filled with argon gas flow, heating to 500 ℃ at the heating speed of 3 ℃/min, sintering at high temperature for 6 hours, and naturally cooling to room temperature to obtain reddish brown iron oxide;
1.2) mixing succinic acid with triethyl hexyl phosphoric acid and an ethanol solvent according to a molar ratio of 1:12:42, and uniformly dispersing by ultrasonic treatment for 3 hours to obtain a succinic acid homogeneous solution;
1.3) mixing the succinic acid homogeneous solution with the iron oxide obtained in the step 1.1) according to a molar ratio of 1:15, stirring at a high speed (the stirring speed is 550rpm/min), dispersing for 50 minutes, coating a layer of carbon source solution on the surface of the iron oxide under the action of a surfactant, heating to 600 ℃ at a heating speed of 3 ℃/min, sintering at a high temperature for 10 hours, and cracking the carbon source solution on the surface of iron oxide particles into a carbon simple substance to form a carbon film layer to cover the surface of the iron oxide;
(2) carbon-coated Li5FeO4The preparation of (1):
2.1) according to Li: fe is 6: 1, mixing the iron oxide coated with the carbon film layer and lithium carbonate, adding 150mL of ethanol, putting the mixture into a nylon tank, mixing the mixture on a ball mill for 4 hours, and performing spray drying (the temperature of an air inlet of a spray dryer is 120 ℃, the temperature of an air outlet of the spray dryer is 120 ℃, and the feeding speed is 5mL/min) to obtain a powdery mixture;
2.2) placing the mixture obtained in step 2.1) into a tube furnace at 6m3Heating to 800 ℃ at the speed of 5 ℃/min under the argon atmosphere for sintering for 15 hours, and then naturally cooling to room temperature along with the furnace to obtain the Li with carbon-coated surface5FeO4；
(3) Carbon and chromium oxide double-layer coated Li5FeO4Preparation:
3.1) coating the surface with Li of the carbon layer5FeO4Adding the powder into a chromium sulfate solution with the concentration of 1.50mol/L according to chromium ions in the chromium sulfate solution and Li of the surface coating carbon layer5FeO4The molar ratio of the components is 1: 25 to prepare a mixture;
3.2) mixing 3.0 mol. L-1Ammonium hydroxide solution is slowly added to the mixture and stirred until the solution is pasty, thereby dissolving in the Li5FeO4A layer of uniform chromium hydroxide is formed on the surface of the carbon layer in situA precipitate layer;
3.3) placing the material obtained in 3.2) in a tube furnace at 6m3Heating to 800 ℃ at the speed of 3 ℃/min in nitrogen atmosphere, sintering for 8 hours, and naturally cooling to room temperature along with the furnace to obtain the carbon and chromium oxide surface double-layer coated Li5FeO4Composite material, labeled S60.
The S60 sample was exposed to air for 3 days and the resulting sample was labeled S63.
Comparative example 1:
the sample of this comparative example was Li5FeO4Labeled as D10, was prepared as follows:
(1) according to the weight ratio of Li: fe-5: 1, mixing iron oxide and lithium oxide, adding 200mL of ethanol, putting the mixture into a nylon tank, mixing the mixture on a ball mill for 3 hours, and performing spray drying (the temperature of an air inlet of a spray dryer is 150 ℃, the temperature of an air outlet of the spray dryer is 130 ℃, and the feeding speed is 6mL/min) to obtain a powdery mixture;
(2) putting the mixture obtained in the step (1) into a tube furnace at 6m3Heating to 850 ℃ at the speed of 5 ℃/min under the argon atmosphere for sintering for 10 hours, and then naturally cooling to room temperature along with the furnace to obtain Li5FeO4。
The D10 sample was exposed to air for a period of 1 day and the resulting sample was labeled D11.
Comparative example 2:
the sample of this comparative example was carbon-coated Li5FeO4Labeled D20, which was prepared identically to steps (1) and (2) of example 1, except that the sonication time in step 1.1) of this comparative example was 10 min; while the time for the sonication in example 1 was 20 min.
Comparative example 3:
the sample of this comparative example is Li in comparative example 15FeO4The sample (labeled as D1) was coated with an alumina layer, and the process and parameters of coating with alumina were the same as those in step (3) of example 1, and Li coated on the surface of the alumina prepared5FeO4Composite material, labeled D30.
The D30 sample was exposed to air for a period of 3 days and the resulting sample was labeled D33.
Comparative example 4:
the comparative example is in Li5FeO4Coated with carbon and Mo2C, the specific preparation process is as follows:
(1) reacting LiOH & H2O and Fe2O3Mixing according to a molar ratio of 10:1, and placing the mixture in a stirring ball mill for mixing and grinding for 8 hours; putting the precursor prepared by fully mixing and grinding into a corundum crucible; putting the crucible into a tube furnace, introducing nitrogen, heating from room temperature at a heating rate of 5 ℃/min to 850 ℃, roasting for 20h, and naturally cooling to room temperature to obtain Li5FeO4A material;
(2) mixing Li5FeO4Mixing with glucose according to the mass ratio of 100:16.3, placing in a stirring ball mill, adding ethanol, and wet mixing and grinding for 6 h; drying the precursor prepared by fully mixing and grinding, and then placing the precursor into a corundum crucible; and (3) putting the crucible into a tube furnace, introducing Ar gas, heating from room temperature at the heating rate of 5 ℃/min, heating to 600 ℃, roasting for 10h, and naturally cooling to room temperature to obtain the Li5FeO4/C material.
(3) Mixing Li5FeO4/C、MoO3Mixing with glucose at a mass ratio of 100:7.4:9.3, placing in a ball mill, adding ethanol, and wet mixing and grinding for 6 h; drying the precursor prepared by fully mixing and grinding, and then placing the precursor into a corundum crucible; introducing argon into the crucible in a tubular furnace, heating at room temperature at a heating rate of 5C/min, heating to 800 deg.C, calcining for 10 hr, and naturally cooling to room temperature to obtain a product with carbon content of 3 wt.%, Mo2Li with a C content of 5 wt.%5FeO4/C/Mo2C three-layer structure composite material, labeled D40.
The D40 samples were exposed to air for 1 day, 2 days, and 3 days, respectively, and the resulting samples were labeled D41, D42, and D43, respectively.
Comparative example 5:
the lithium ion positive electrode material of the comparative example contains a lithium supplement additive comprising Li5FeO4Matrix, lithium-coated5FeO4A first coating carbon layer on the surface of the substrate and a second coating alumina layer on the surface of the first coating; wherein the mass of the carbon layer is Li5FeO42.3 wt% of the mass of the matrix; alumina relative to Li5FeO43.3 wt% of the mass of the matrix.
The preparation method of the lithium ion cathode material lithium supplement additive of the comparative example comprises the following steps:
(1) carbon-coated Li5FeO4The preparation of (1):
1.1) according to Li: fe-5: 1, mixing iron oxide and lithium hydroxide, dissolving in deionized water, and then mixing according to a molar ratio of glucose to iron oxide of 1:10, putting the mixture into a nylon tank, mixing the mixture on a ball mill for 3 hours, and performing spray drying (the temperature of an air inlet of a spray dryer is 150 ℃, the temperature of an air outlet of the spray dryer is 100 ℃, and the feeding speed is 10mL/min) to obtain a powdery mixture;
1.2) placing the mixture obtained in 1.1) in a tube furnace at 6m3Heating to 850 ℃ at the speed of 5 ℃/min under the argon atmosphere, sintering for 15 hours, and then naturally cooling to room temperature along with the furnace to obtain the Li with carbon-coated surface5FeO4。
(2) Carbon and alumina double-layer coated Li5FeO4Preparation:
2.1) coating Li of the surface carbon layer obtained in 1.2)5FeO4Adding the powder into an aluminum sulfate solution with the concentration of 1mol/L, and according to the aluminum ions in the aluminum sulfate solution and Li of the surface-coated carbon layer5FeO4In a molar ratio of 1:10 to form a mixture;
2.2) the concentration is 0.5 mol.L-1Ammonium hydroxide solution is slowly added to the mixture and stirred until the solution is pasty, thereby dissolving in the Li5FeO4Forming a uniform aluminum hydroxide precipitate layer on the surface of the carbon layer in situ;
2.3) placing the material obtained in 2.2) in a tube furnace at 3m3Heating to 700 ℃ at the speed of 3 ℃/min under the argon atmosphere, sintering for 6 hours, and then naturally cooling to the temperatureAt room temperature, the carbon and aluminum oxide double-layer coated Li can be obtained5FeO4Composite material, labeled D50.
The D50 sample was exposed to air for 1 day and the resulting sample was labeled D51.
Comparative example 6:
the lithium ion positive electrode material of the comparative example contains a lithium supplement additive comprising Li5FeO4Matrix, located in Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating alumina layer on the surface of the first coating; wherein the mass of the carbon layer is Li5FeO42.3 wt% of the mass of the matrix; alumina relative to Li5FeO43.3 wt% of the mass of the matrix.
The preparation method of the lithium ion cathode material lithium supplement additive of the comparative example comprises the following steps:
(1) carbon-coated Li5FeO4The preparation of (1):
1.1) according to LiOH: fe2O3: glucose 100: 10:1, mixing lithium hydroxide, ferric oxide and glucose, putting the mixture into a nylon tank, and mixing the mixture for 3 hours on a ball mill to obtain a powdery mixture;
1.2) placing the mixture obtained in step 1.1) into a tube furnace at 6m3Heating to 850 ℃ at the speed of 5 ℃/min under the argon atmosphere for sintering for 15 hours, and then naturally cooling to room temperature along with the furnace to obtain the Li with carbon-coated surface5FeO4；
(2) Carbon and alumina surface coated Li5FeO4Preparation:
2.1) mixing alumina according to the weight ratio of 1:20 mol ratio to 1.2) to obtain surface carbon-coated Li5FeO4Mixing the powders, placing the mixture in a ball mill, and mixing and grinding the mixture for 6 hours;
2.2) placing the mixture obtained in 2.1) in a tube furnace at 3m3Heating to 700 ℃ at the speed of 3 ℃/min under the argon atmosphere for sintering for 6 hours, and then naturally cooling to room temperature along with the furnace to obtain carbon and aluminum oxide double-layer coated Li5FeO4Composite material, labeled D60.
The D60 sample was exposed to air for a period of 3 days and the resulting sample was labeled D63.
The test method comprises the following steps:
the prepared samples of the respective examples and comparative examples, conductive carbon black and PVDF binder were mixed at a mass ratio of 8: 1:1, then stirring for 2 hours, and adjusting to slurry. And coating the slurry on an aluminum foil by using a coating machine to prepare an electrode, compacting the electrode by using a roller press, and punching the compacted composite material electrode into an electrode wafer with the thickness of 12mm by using a sheet punching machine. And (3) drying the electrode wafer in a vacuum drying oven at 120 ℃ for 12h to obtain the positive plate. The electrolyte is 1.2mol/L LiPF 6/EC-DMC (1:1), a positive plate and a lithium metal plate are respectively used as a positive electrode and a negative electrode, a celgard2300 polypropylene microporous film is used as a diaphragm, and a lithium battery is assembled in a glove box filled with high-purity argon.
A LAND battery test system is adopted, the voltage range is 2.0-4.5V, the current density is 45mA/g, and the first charge-discharge specific capacity of the battery is recorded as shown in table 2.
The battery samples of examples 1 to 6 and comparative examples 1 to 6 were prepared in this order by the above-described method, and the respective numbers CS10, CS13, CS20, CS23, CS30, CS33, CS40, CS43, CS50, CS53, CS60, CS63, CD10, CD13, CD20, CD23, CD30, CD33, CD40, CD43, CD50, CD53, CD60, and CD63, and the first charge-discharge capacity and residual lithium content of each battery sample are shown in table 2.
TABLE 1 conductivity test results
Test items S10 S20 S30 S40 S50 S60 D10 D20 D30 D40 D50 D60
ρ-1(S cm-1) 1.71 1.65 1.42 1.58 1.46 1.69 10-9 1.18 10-3 1.43 1.54 1.38
TABLE 2 first charge-discharge capacity and surface residual lithium test results
Figure BDA0002201078960000141
Figure BDA0002201078960000151
Table 1 shows the electrical conductivity of the additives of each example and comparative example. As can be seen from the results of Table 1, Li not coated with any material5FeO4Has an electrical conductivity of 10-9S/cm, almost an insulator, double-layered coated on the surface of Li by carbon and transition metal oxide5FeO4The uniform and compact coating layer can be formed on the surface of the particle, so that the coating layer forms a conductive network, and the Li can be obviously improved5FeO4Conductivity of material, carbon and aluminium oxide double-layer coating Li5FeO4When the conductivity of the material is maximum, the conductivity is as high as 1.71S/cm.
Table 2 shows the first charge and discharge capacity and residual lithium content of the batteries manufactured using the materials of the respective examples and comparative examples. From the results in table 2, it can be seen that the first charge-discharge specific capacities of the battery samples CS10, CS20, CS30, CS50 and CS60 are almost the same as the first charge-discharge specific capacities of the battery samples CS13, CS23, CS33, CS53 and CS63 assembled after being placed for three days, and the residual lithium is almost unchanged, which indicates that the S1, S2, S3, S4, S5 and S6 samples assembled after being placed for three days have good stability, and the first charge-discharge specific capacities of the battery samples CD53 and CD63 assembled after being placed for three days are obviously reduced from the first charge-discharge specific capacities of the battery samples CD53 and CD63, which indicates that the air water can be effectively isolated from Li by wet double-layer coating5FeO4Corrosion of the material, thereby causing the carbon and transition metal oxide bilayer to coat Li5FeO4The material has extremely high stability, but the dry double-layer coating cannot achieve a perfect coating effect, and a sample can slowly deteriorate after being placed in the air, so that the air stability is poor. In comparative example 1, since the CD1 sample was not coated, the specific charge capacity was only 330.9mAh/g, the residual lithium increased from 4.584% to 53.472%, the material was completely deteriorated after being left for three days, and the stability was very poor; in comparative example 2, Li5FeO4The surface of the material is singly coated with carbon by a wet method, the charging capacity of a CD20 sample reaches 617.4mAh/g, and the capacity is exerted; but in comparative example 3 Li alone5FeO4The surface of the material is coated with the transition metal oxide, so that a perfect coating effect cannot be achieved, the specific charge capacity of a sample is obviously reduced after the material is placed for 3 days, the charge capacity is only 410.8mAh/g, the residual lithium is increased to 2.162% from 0.487%, the D30 material is poor in stability, and the importance of the carbon and the transition metal oxide in wet coating together is proved; in comparative example 4, Li was prepared by the method of example 4 of application No. 201710763680.65FeO4/C/Mo2C composite, conductivity of D40 sample was 1.43S cm-1The specific charge capacity of the CD40 sample is 608.7mAh/g, and Mo is inevitably caused by higher synthesis temperature2The sintering and agglomeration of C can cause incomplete reaction at a lower temperature, which can affect the coating effect to a certain extent, and the residual lithium is increased from 0.415% to 1.103%, so that the capacity of the battery assembled by the sample D43 after being placed for three days is attenuated to a certain extent, only 571.9mAh/g, the stability of the D4 series samples in air is general, and the samples can slowly absorb water and deteriorate when being placed in air. And double-layer coating of Li by wet method5FeO4Can overcome the problem and ensure that the carbon source and the transition metal oxide are uniformly plated on the Li5FeO4The surface of the material forms a uniform and compact coating layer, which greatly improves the air stability and the conductivity of the material.
FIG. 1 XRD patterns of S10, S11, S12 and S13 samples in example 1 of the present invention, from which it can be seen that the S1 series samples are made of Li5FeO4And small amounts of C and Al2O3The compositions of S11, S12 and S13 samples obtained by respectively placing for 1 day, 2 days and 3 days in the air are almost the same as the compositions of S10, which indicates that the S1 material has good air stability, good coating effect and no water absorption and deterioration. This indicates that the material has a relatively high air stability, C and Al2O3Double-layer coated Li5FeO4 can effectively reduce Li in the composite material5FeO4The contact area of the particles with the outside air,effectively inhibit Li5FeO4Reactivity of the material with water.
FIG. 2 is a first charge and discharge curve of battery samples S10 and S13 at a current density of 45 mA/g. As can be seen from the graph, the first charge capacity of S10 is 657.9mAh/g, the first discharge capacity is 81.6mAh/g, the first charge capacity of S13 is 653.2mAh/g, and the first discharge capacity is 93.3 mAh/g. The charge and discharge capacity of the battery S13 and the capacity of the battery S10 are almost the same, which shows that the S1 sample is not deteriorated and is very stable after being placed in the air for 3 days.

Claims (10)

1. The lithium ion positive electrode material lithium supplement additive is characterized by comprising Li5FeO4Matrix and Li site5FeO4A coating layer on the surface of the substrate; the coating layer includes Li5FeO4A first coating carbon layer on the surface of the substrate and a second coating transition metal oxide layer on the surface of the first coating.
2. The lithium supplement additive of claim 1, wherein the transition metal oxide is selected from the group consisting of oxides of one or more elements of Ti, Al, Zn, Cr, V, Zr, Mg.
3. The lithium supplement additive of claim 1, wherein the first clad carbon layer has a mass of Li5FeO41-5 wt% of the matrix mass; the second cladding layer transition metal oxide layer is opposite to Li5FeO41-10 wt% of the matrix mass.
4. A method for preparing a lithium supplementing additive as claimed in any one of claims 1 to 3, comprising the steps of:
(1) adding ferric oxide into the organic carbon source homogeneous dispersion liquid, stirring and dispersing uniformly, and then carrying out heat treatment to obtain ferric oxide coated by the carbon layer;
(2) wet mixing and spraying the iron oxide coated by the carbon layer obtained in the step (1) and a lithium sourceDrying to obtain powdery mixture, then carrying out high-temperature sintering under the protection of inert gas, and naturally cooling to room temperature along with the furnace to obtain Li with carbon-coated surface5FeO4；
(3) Surface carbon-coated Li5FeO4Adding the mixture into a salt solution containing transition metal ions, adding an ammonium hydroxide solution, stirring uniformly, then sintering at high temperature under the protection of inert gas, and naturally cooling to room temperature along with a furnace to obtain Li with double-layer coating of carbon and transition metal oxide layers5FeO4Namely the lithium supplement additive.
5. The preparation method according to claim 4, wherein in the step (1), the organic carbon source homogeneous dispersion liquid is obtained by mixing an organic carbon source, a surfactant and an ethanol solvent, and performing ultrasonic dispersion uniformly; the organic carbon source is one or more of glucose, fructose, sucrose, soluble starch, succinic acid, citric acid, lactic acid and acetic acid; the surfactant is one or more of oleic acid, tetracosanoic acid, perfluorocarboxylic acid, silicone oil, polyether, triethylhexyl phosphoric acid and fatty acid.
6. The method according to claim 4, wherein in the step (1), the iron oxide is obtained by the following production method: adding a ferric iron salt solution into an ammonium hydroxide solution, stirring and dispersing, then carrying out ultrasonic treatment, standing, and then washing and heating the obtained precipitate to obtain reddish brown iron oxide; wherein the ferric salt solution is one or more of ferric nitrate solution, ferric sulfate solution, ferric chloride solution and ferric bromide solution, and the concentration of the solution is 0.5-4 mol g-1(ii) a The molar ratio of the trivalent ferric salt solution to the ammonium hydroxide solution is 1: 1-1: 3; the stirring speed is 100-500rpm, the stirring time is 20-60 minutes, the ultrasonic treatment frequency is 20-30Hz, and the treatment time is 10-30 minutes.
7. The method according to any one of claims 4 to 6, wherein the weight ratio of the organic carbon source to the iron oxide is 1:20 to 1: 10.
8. The method according to any one of claims 4 to 6, wherein in the step (1), the stirring speed is 200 and 800rpm, and the stirring time is 20 to 50 minutes; the heat treatment is to heat the mixture to 300-700 ℃ at a heating rate of 1-5 ℃/min and to sinter the mixture for 0.5-3 hours.
9. The method according to any one of claims 4 to 6, wherein in the step (2), the molar ratio of the lithium source to the iron oxide is (9-11: 1; during spray drying, the temperature of an air inlet is 150-200 ℃, the temperature of an air outlet is 100-150 ℃, and the feeding speed is 5-20 mL/min; the high-temperature sintering is to heat up to 650-900 ℃ at a heating rate of 1-10 ℃/min and to preserve heat for 3-10 h.
10. The method according to any one of claims 4 to 6, wherein in the step (3), the high-temperature sintering is performed by heating to 700 to 800 ℃ at a heating rate of 1 to 5 ℃/min and sintering for 5 to 10 hours; the molar ratio of the ammonium hydroxide solution to the metal ions in the transition metal ion salt is (1:1) - (3: 1); metal ion and Li of surface coating carbon layer in solution of transition metal ion salt5FeO4The molar ratio of (1: 10) to (1: 40).
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CN115347162A (en) * 2022-07-26 2022-11-15 深圳市德方创域新能源科技有限公司 Lithium-supplement composite material, preparation method thereof, positive electrode material and secondary battery
WO2024021231A1 (en) * 2022-07-28 2024-02-01 广东邦普循环科技有限公司 Preparation method for high-capacity battery active material and use thereof
WO2024078414A1 (en) * 2022-10-09 2024-04-18 深圳市德方创域新能源科技有限公司 Lithium replenishing additive for positive electrode and preparation method therefor, lithium-rich positive electrode, and secondary battery
CN115719808B (en) * 2022-12-06 2024-06-04 湖北万润新能源科技股份有限公司 Preparation method and application of lithium ferrite lithium supplementing agent
CN115719808A (en) * 2022-12-06 2023-02-28 湖北万润新能源科技股份有限公司 Preparation method and application of lithium ferrite lithium supplement agent
WO2024140843A1 (en) * 2022-12-30 2024-07-04 比亚迪股份有限公司 Lithium-supplementing material, positive electrode, electrochemical apparatus, and electric device
WO2024140106A1 (en) * 2022-12-31 2024-07-04 湖北亿纬动力有限公司 Positive electrode lithium-supplementing agent, lithium-ion battery, and formation method for pre-lithiation of positive electrode thereof
CN116409822A (en) * 2023-03-01 2023-07-11 广东邦普循环科技有限公司 Preparation method of lithium battery anode material additive
CN116409822B (en) * 2023-03-01 2024-09-06 广东邦普循环科技有限公司 Preparation method of lithium battery anode material additive
CN117317415A (en) * 2023-11-15 2023-12-29 银贮(宁波)科技有限公司 Carbon-coated lithium ferrate lithium supplementing additive and preparation method thereof
CN117865226A (en) * 2024-03-13 2024-04-12 天能帅福得能源股份有限公司 Positive electrode lithium supplementing additive, preparation method thereof and lithium ion battery

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