CN110233262B - Halogen element O-site doped nickel oxide and preparation method thereof, target material, thin film material, lithium battery cathode, lithium battery and electric equipment - Google Patents

Halogen element O-site doped nickel oxide and preparation method thereof, target material, thin film material, lithium battery cathode, lithium battery and electric equipment Download PDF

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CN110233262B
CN110233262B CN201910595607.1A CN201910595607A CN110233262B CN 110233262 B CN110233262 B CN 110233262B CN 201910595607 A CN201910595607 A CN 201910595607A CN 110233262 B CN110233262 B CN 110233262B
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lithium battery
nickel oxide
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film material
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CN110233262A (en
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王佳希
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Yuyao Haitai Trading Co ltd
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Thornton New Energy Technology Changsha Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H01M4/0426—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides halogen element O-site doped nickel oxide, a preparation method thereof, a target material, a thin film material, a lithium battery cathode, a lithium battery and electric equipment, and relates to the field of new materials. The preparation method of the halogen element O-site doped nickel oxide comprises the following steps: dissolving nickel salt and halogen salt in acid, heating to prepare dry gel, and calcining the dry gel. The halogen element O-site doped nickel oxide is prepared by the preparation method. The target material is obtained by sintering nickel oxide doped with halogen element O site. The film material comprises: a carbon nanotube film and an active material layer disposed on the surface of the carbon nanotube film. A lithium battery negative electrode includes a thin film material. A lithium battery includes a lithium battery negative electrode. The electric equipment comprises a lithium battery. The halogen element O site is doped with nickel oxide, so that the conductivity of NiO is effectively improved, and the internal resistance is reduced. The film material has high capacity, high energy density and high multiplying power. The lithium battery prepared by using the film material has good cycle performance and safety performance.

Description

Halogen element O-site doped nickel oxide and preparation method thereof, target material, thin film material, lithium battery cathode, lithium battery and electric equipment
Technical Field
The invention relates to the field of new materials, in particular to halogen element O-site doped nickel oxide, a preparation method thereof, a target material, a thin film material, a lithium battery cathode, a lithium battery and electric equipment.
Background
With the rapid development of electronic devices, people have higher and higher requirements on batteries, and the thinning of the batteries is an inevitable trend in the development of future lithium batteries on the premise of ensuring high capacity and high energy density. The NiO negative electrode material of the lithium ion battery is much higher than the current commercial graphite negative electrode material in theoretical capacity 718mAh/g, and has the advantages of simple preparation method, abundant raw material sources, environmental friendliness, high theoretical capacity, good safety performance and the like, and is widely concerned by researchers.
However, NiO negative electrode materials of lithium ion batteries also have the problems of improved conductivity and high internal resistance, and the problems are also main reasons for restricting the development of the NiO negative electrode materials.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of halogen element O-site doped nickel oxide, which effectively improves the conductivity and reduces the internal resistance of nickel oxide by doping halogen element anions.
The second purpose of the invention is to provide a halogen element O-site doped nickel oxide prepared by the method.
The third object of the present invention is to provide a target material obtained by sintering the above-mentioned halogen element O-site-doped nickel oxide.
The fourth purpose of the invention is to provide a film material which has good cycle stability, small volume expansion, high multiplying power and high first efficiency.
The fifth purpose of the invention is to provide a lithium battery negative electrode, which comprises the film material.
The sixth purpose of the invention is to provide a lithium battery which has high capacity, high energy density, safety and environmental protection.
The seventh purpose of the invention is to provide an electric device, which comprises the lithium battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of halogen element O-site doped nickel oxide comprises the following steps:
dissolving nickel salt and halogen salt in acid, heating to prepare xerogel, and calcining the xerogel to obtain O-site doped nickel oxide of halogen elements.
The method comprises the steps of processing nickel salt and halogen salt by a gel method to obtain dry gel, doping halogen negative ions into NiO by calcining to obtain an O-site doped NiO target, doping trace anions at the O site of the NiO to change the electronic structure of the NiO to form a corresponding N-type semiconductor or P-type semiconductor, effectively improving the conductivity of the NiO and reducing the internal resistance of the NiO.
Halogen elements have strong oxidizing properties and are easy to substitute for the O site.
Preferably, the halide salt is a fluoride salt.
The ionic radius of the F ion is closer to that of oxygen, the O position is more easily replaced, and the formed dopant structure is more stable.
More preferably, the fluoride salt is lithium fluoride.
The closer the ionic radius is to O, the better the doping effect is, and the more stable the obtained dopant structure is.
Preferably, the nickel salt comprises at least one of basic nickel carbonate and nickel hydroxide.
Preferably, said nickel salt and said halide salt are in the form of NiZXyO1-yPreparing materials, wherein y is 0.01-0.1, and X is halogen elements.
The types and the mixture ratio of the nickel salt and the halogen salt are optimized, so that the performance of the target material can be further optimized.
Preferably, the acid is nitric acid.
Nitric acid is easy to decompose by heating, impurity elements cannot be introduced, and the doping effect of the target material can be better ensured.
Preferably, after dissolving the nickel salt and the halogen salt in an acid and before the heating to form a xerogel, the method further comprises:
adjusting the pH value of the system to 6-8.
The pH is adjusted to be about neutral so as to prevent corrosion caused by over-strong acidity; in addition, volatile acids are prevented from volatilizing.
More preferably, ammonia is used to adjust the pH of the system.
Ammonia water is used for adjusting the pH value, ammonia gas is easy to volatilize after reaction, and other impurities are not easy to introduce.
Further preferably, the method further comprises adding a dispersant to the system after adjusting the pH of the system and before heating to form a xerogel.
The use of the dispersing agent is beneficial to the uniform distribution of ions and ensures the uniform performance of the target material.
More preferably, the dispersant is polyvinyl alcohol and/or citric acid.
The dispersing agent is preferred in order to further optimize the effect of the uniform distribution.
Preferably, the calcining temperature is 800-900 ℃ and the time is 9-18 h.
The temperature and time of the calcination are controlled to optimize the progress of the doping.
Preferably, the calcination further comprises a glue discharging step before calcination.
More preferably, the temperature of the gel discharging is 250-350 ℃, and the time is 5-15 h.
The main purpose of the binder removal is to remove impurities, such as water and by-products, therefrom. The temperature and time are controlled to optimize the effect of the rubber discharging.
The halogen element O-site doped nickel oxide is prepared by the preparation method.
The target material is obtained by sintering the O-site doped nickel oxide of the halogen element.
Preferably, the sintering temperature is 1200-1400 ℃, and the time is 64-90 h.
A film material is prepared by the following steps:
a carbon nanotube film and an active material layer provided on a surface of the carbon nanotube film, the active material layer comprising the halogen element O-site-doped nickel oxide according to claim 14.
A layer of halogen element O-site doped nickel oxide active material is arranged on the surface of the carbon nano tube film, and the film formation and the nano formation can effectively reduce the volume expansion coefficient of the carbon nano tube film. Compared with the traditional copper foil, the carbon nanotube film has good conductivity and larger specific surface area, the high specific surface area can greatly increase the specific surface area of the active substance, so that the energy density of the material is improved, and in addition, the high specific surface area increases the contact area between the carbon nanotube film and the electrolyte, so that the rate capability of the battery is improved.
Preferably, the tube diameter of the carbon nanotube in the carbon nanotube film is less than or equal to 6 nm.
The diameter of the carbon nano tube has obvious influence on the conductivity, so the diameter of the carbon nano tube is controlled to be less than or equal to 6 nm.
More preferably, the carbon nanotube is a helical carbon nanotube.
The helical carbon nanotube refers to the direction vector C of the atomic arrangement on the carbon nanotubeh＝na1+ma22n + m is 3q (q is an integer), that is, 2n + m is an integer multiple of 3. The carbon nano tube with the specific structure has better conductivity, smaller internal resistance and better rate capability. In addition, the large length-diameter ratio enables the carbon nano tube to have better heat-conducting property, so that the heat dissipation of the battery cell in the use process is more uniform.
Preferably, the carbon nanotube film is cleaned before use.
More preferably, the cleaning process includes: and putting the carbon nano tube film into ethanol or acid solution for ultrasonic treatment, and then cleaning and drying the carbon nano tube film by using water.
The main purpose of cleaning is to remove contaminants from the surface of the carbon nano-film.
Preferably, the active material layer is obtained by depositing a target material on the surface of the carbon nanotube film, and the target material is obtained by sintering the halogen element O-site doped nickel oxide.
The deposition mode of the target material can better control the distribution of the halogen element O-site doped nickel oxide on the surface of the carbon nano tube film and optimize the electrical property of the carbon nano tube film.
Preferably, the deposition is performed using a magnetron sputtering process.
The magnetron sputtering technology can further effectively reduce the volume expansion coefficient of the NiO cathode material through thinning, and improve the cycle performance and the safety performance of the NiO cathode material.
More preferably, the process parameters of the magnetron sputtering process are controlled as follows:
ar and O2Is 1: 3 to 5, the pressure is 0.6 to 1.0Pa, and the sputtering time is 1.5 to 2.5 hours.
Compared with the coating process in the current industrial production, the magnetron sputtering technology is easier to adjust the thickness of the film through parameter change; the uniformity of the film is more stable, and the adhesion of the active substance and the current collector is obviously enhanced; according to different sputtering rates of different elements, the proportion of each element of the active substance can be controlled by adjusting parameters; the valence state of some elements can be effectively controlled according to different sputtering atmospheres; the density of the magnetron sputtering film is far higher than that of the magnetron sputtering film prepared by a common coating process, so that the energy density of the material can be increased.
Optionally, the active material layer has a thickness of 5 to 10 μm.
The thickness of the active substance in the film material is optimized, so that the performance of the lithium battery cathode and the lithium battery which are manufactured subsequently can be further ensured.
A lithium battery negative electrode comprises the film material.
A lithium battery comprises the lithium battery cathode.
An electric device comprises the lithium battery.
Compared with the prior art, the invention has the beneficial effects that:
1. halogen negative ions are doped into the NiO to obtain O-site doped NiO, so that the conductivity of the NiO is effectively improved, and the internal resistance is reduced;
2. the halogen element O site is doped with nickel oxide to prepare a target material, which is beneficial to the subsequent processing of a film material and can obtain a film cathode material with better electrical property;
3. a layer of O-site doped NiO active substance is deposited on the surface of the carbon nanotube film, so that the volume expansion coefficient of the carbon nanotube film can be effectively reduced through film formation and nanocrystallization, and the energy density of the material is improved;
4. the lithium battery has good cycle performance, improved rate performance, small volume change and high safety factor;
5. the lithium battery prepared by the lithium battery cathode provided by the application is used for supplying power, and is long in service life, safe and stable.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is an XRD spectrum of NiO ceramic and the target and thin film materials obtained in example 4;
fig. 2 is a cycle performance graph of the button cell obtained in example 4 at 0.2C rate;
fig. 3 is a diagram showing the relationship between the cycle number and specific capacity of a button cell prepared from a common NiO negative electrode material.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Nickel hydroxide and lithium fluoride are mixed according to NiZFyO1-yWeighing electrochemical coefficients according to a molar ratio of (y is 0.1, and Z is 1.9), dissolving nickel hydroxide and lithium fluoride in dilute nitric acid, adjusting the pH value to be neutral by ammonia water, and heating and stirring for 20 hours until xerogel is formed.
And fully grinding the gel in a mortar, and calcining the gel in a muffle furnace at 850 ℃ for 15h to obtain the fluorine O position doped nickel oxide.
Grinding and granulating the fluorine O position doped nickel oxide, pressing into a wafer with the diameter of 70mm and the thickness of 7mm, sintering in a muffle furnace at 1350 ℃ for 75h for molding, and finally grinding the wafer into a target with the diameter of 50mm and the thickness of 5 mm.
Depositing the prepared target on the surface of the spiral carbon nanotube film with the pipe diameter less than or equal to 6nm by utilizing a magnetron sputtering method, and controlling the atmosphere to be Ar: o is21: and 4, the pressure is 0.8Pa, the sputtering time is 2h, and thus the film material with the thickness of 6 mu m of the fluorine O site doped NiO deposited on the surface of the carbon nano tube film is obtained, wherein the fluorine O site doped NiO forms an active material layer.
And (3) preparing a lithium battery cathode by using the film material, and then preparing the lithium battery.
The lithium battery can be used for processing to obtain electric equipment.
Example 2
Basic nickel carbonate and lithium fluoride are mixed according to NiZFyO1-yWeighing the molar ratio of electrochemical coefficients (y is 0.02, and Z is 1.98), dissolving basic nickel carbonate and lithium fluoride in dilute nitric acid, adjusting the pH value to 6 with ammonia water, adding polyvinyl alcohol for dispersing, heating and stirring for 20 hours until dried gel is formed, and completely dissolving PVA in the process. Then carrying out glue discharging treatment for 15h at 250 ℃ to remove redundant water and byproducts.
And fully grinding the gel in a mortar, and calcining the gel in a muffle furnace at 900 ℃ for 9 hours to obtain fluorine O-site doped nickel oxide.
Grinding, granulating and pressing the fluorine O position doped nickel oxide into a wafer, sintering the wafer in a muffle furnace at 1200 ℃ for 90 hours for forming, and finally grinding the wafer into a target material.
Placing the spiral carbon nanotube film with the pipe diameter less than or equal to 6nm in a dilute hydrochloric acid solution for ultrasonic cleaning for 10min, then cleaning in clear water for more than 3 times, and drying for later use.
Depositing the prepared target on the surface of the carbon nano tube film by utilizing a magnetron sputtering method, wherein the atmosphere is Ar: o is21: and 3, the pressure is 1.0Pa, and the sputtering time is 2.5h, so that the film material with the thickness of 10 mu m of fluorine O site doped NiO deposited on the surface of the carbon nano tube film is obtained.
And (3) preparing a lithium battery cathode by using the film material, and then preparing the lithium battery.
The embodiment also provides electric equipment, and the electric equipment comprises the lithium battery.
Example 3
Basic nickel carbonate and nickel hydroxide (the mol ratio of the basic nickel carbonate to the nickel hydroxide)1: 1) lithium fluoride according to NiZFyO1-yWeighing the electrochemical coefficient molar ratio (y is 0.01, Z is 1.99), dissolving the basic nickel carbonate, the nickel hydroxide and the lithium fluoride in dilute nitric acid, adjusting the pH value to 8 by ammonia water, adding polyvinyl alcohol and citric acid for dispersion, and heating and stirring for 20 hours until the xerogel is formed. Then, carrying out glue discharging treatment for 5h at 350 ℃ to remove redundant water and byproducts.
And fully grinding the gel in a mortar, and calcining the gel in a muffle furnace at 800 ℃ for 18h to obtain fluorine O-site doped nickel oxide.
Grinding, granulating and pressing the fluorine O position doped nickel oxide into a wafer, sintering the wafer in a muffle furnace at 1400 ℃ for 64h for forming, and finally grinding the wafer into a target material.
Placing the spiral carbon nanotube film with the pipe diameter less than or equal to 6nm in an ethanol water solution for ultrasonic cleaning for 15min, then cleaning in clear water for more than 3 times and drying for later use.
Depositing the prepared target on the surface of the carbon nano tube film by utilizing a magnetron sputtering method, wherein the atmosphere is Ar: o is21: and 5, the pressure is 0.6Pa, and the sputtering time is 1.5h, so that the film material with the thickness of 5 mu m of fluorine O site doped NiO deposited on the surface of the carbon nano tube film is obtained.
And (3) preparing a lithium battery cathode by using the film material, and then preparing the lithium battery.
The embodiment also provides electric equipment, and the electric equipment comprises the lithium battery.
Example 4
Basic nickel carbonate and lithium fluoride are mixed according to NiZFyO1-yWeighing the molar ratio of electrochemical coefficients (y is 0.05, and Z is 1.95), dissolving basic nickel carbonate and lithium fluoride in dilute nitric acid, adjusting the pH value to 7 by ammonia water, adding citric acid for dispersing, and heating and stirring for 20 hours until xerogel is formed. Then, carrying out glue discharging treatment for 10h at 300 ℃ to remove redundant water and byproducts.
And fully grinding the gel in a mortar, and calcining the gel in a muffle furnace at 850 ℃ for 15h to obtain fluorine O-site doped nickel oxide.
Grinding, granulating and pressing the fluorine O-site doped nickel oxide into a wafer, sintering the wafer in a muffle furnace at 1350 ℃ for 75h for forming, arranging a plurality of heat preservation points to prevent the wafer from deforming and cracking, and finally grinding the wafer into a target material.
Placing the spiral carbon nanotube film with the pipe diameter less than or equal to 6nm in dilute hydrochloric acid for ultrasonic cleaning for 10min, then cleaning in clear water for more than 3 times, and drying for later use.
Depositing the prepared target on the surface of the carbon nano tube film by utilizing a magnetron sputtering method, wherein the atmosphere is Ar: o is21: 4, the pressure is 0.8Pa, the sputtering time is 2h, and thus the film material with the thickness of 8 μm of fluorine O site doped NiO deposited on the surface of the carbon nano tube film is obtained.
And (3) preparing a lithium battery cathode by using the film material, and then preparing the lithium battery.
The embodiment also provides electric equipment which uses the lithium battery for power supply.
The lithium battery provided by the application can be used for partially supplying power to electric equipment.
For NiO ceramics (Pure NiO), NiZFyO1-yTarget material (Ni)ZFyO1-ybulk) and thin film material (Ni)ZFyO1-yfilm) was subjected to XRD measurement, and the obtained spectrum was as shown in FIG. 1.
As can be seen from fig. 1, the XRD pattern is consistent and free of impurity phases, indicating that the F element has been doped into the crystal lattice and the substitution is successful, and no second phase is formed.
The cycling performance of the button cell obtained in example 3 at 0.2C rate was tested, and the results are shown in fig. 2 (the abscissa is the cycle number, the left ordinate is the specific capacity, and the right ordinate is the coulombic efficiency). Note that the upper horizontal line represents coulombic efficiency, the left and lower curves represent specific capacity, and the charge and discharge curves overlap.
As can be seen from FIG. 2, the retention rate of the lithium battery prepared from the thin film material provided by the present application reaches as high as 94% after 100 cycles.
Comparative example 1
And (4) using a common NiO negative electrode material to prepare the button cell.
The retention rate of the button cell after 100 cycles was tested and the results are shown in fig. 3 (the abscissa is the cycle number and the ordinate is the specific capacity). As can be seen from fig. 3, the retention rate of the button cell made of the common NiO negative electrode material after 100 cycles is only 50%.
As can be seen from comparison between fig. 2 and fig. 3, after the thin film material prepared from the target material provided by the present application is made into a lithium battery, the initial specific capacity and the specific capacity after 100 cycles are both higher than those of a lithium battery prepared from the conventional nickel oxide negative electrode material.
According to the target material provided by the application, the halogen negative ions are doped into the NiO to obtain the O-site doped NiO target material, so that the conductivity of the target material is effectively improved, and the internal resistance is reduced; and then depositing a layer of O-site-doped NiO active substance on the surface of the carbon nanotube film to obtain the film material, wherein the volume expansion coefficient of the film material is effectively reduced, and the energy density of the material is improved. The lithium battery cathode is prepared by using the film material, so that the lithium battery is prepared, the cycle performance is good, the rate performance is improved, the volume change is small, and the safety coefficient is high; the lithium battery prepared by the lithium battery cathode provided by the application is used for supplying power, and is long in service life, safe and stable.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (8)

1. A thin film material for a negative electrode of a lithium battery, comprising:
the carbon nanotube film and the active substance layer arranged on the surface of the carbon nanotube film, wherein the active substance layer comprises halogen element O-site doped nickel oxide, and the preparation method of the halogen element O-site doped nickel oxide comprises the following steps:
dissolving nickel salt and villiaumite in nitric acid, adjusting the pH value of a system to 6-8 by using ammonia water, adding a dispersing agent into the system, heating to prepare dry gel, and calcining after gel discharge to obtain O-site doped nickel oxide of the halogen element; the calcining temperature is 800-900 ℃, and the time is 9-18 h; the temperature of the glue discharging is 250-350 ℃, and the time is 5-15 h; the fluorine salt is lithium fluoride, the nickel salt comprises at least one of basic nickel carbonate and nickel hydroxide, and the nickel salt and the fluorine salt are NiZXyO1-yA furnish, wherein y =0.01-0.1, z =1.9, 1.95, 1.98, or 1.99, and X is F; the dispersing agent is polyvinyl alcohol and/or citric acid;
the pipe diameter of a carbon nano tube in the carbon nano tube film is less than or equal to 6nm, and the carbon nano tube is a spiral carbon nano tube; the active substance layer is obtained by depositing a target material on the surface of the carbon nano tube film, and the target material is obtained by sintering the halogen element O-site doped nickel oxide; the sintering temperature is 1200-1400 ℃, and the time is 64-90 h.
2. The film material of claim 1, wherein the carbon nanotube film is cleaned before use, and the cleaning process comprises: and putting the carbon nano tube film into ethanol or acid solution for ultrasonic treatment, and then cleaning and drying the carbon nano tube film by using water.
3. The thin film material of claim 1, wherein the depositing is performed using a magnetron sputtering process.
4. The thin film material of claim 3, wherein the process parameters of the magnetron sputtering process comprise:
ar and O2Is 1: 3 to 5, the pressure is 0.6 to 1.0Pa, and the sputtering time is 1.5 to 2.5 hours.
5. A film material according to any one of claims 1 to 4, wherein the thickness of said active material layer is 5 to 10 μm.
6. A negative electrode for a lithium battery, comprising the thin film material for a negative electrode for a lithium battery as claimed in any one of claims 1 to 5.
7. A lithium battery comprising the negative electrode for a lithium battery according to claim 6.
8. An electric device characterized by comprising the lithium battery according to claim 7.
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