CN109449408B - Ferric fluoride-titanium suboxide composite positive electrode material and preparation method and application thereof - Google Patents
Ferric fluoride-titanium suboxide composite positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an iron fluoride-titanium dioxide composite positive electrode material and a preparation method and application thereof. According to the invention, titanium suboxide and a carbon material are jointly used for modifying iron fluoride particles in a spray drying mode to form the composition of point contact inside a bulk phase and surface contact outside the bulk phase, so that a multi-level spherical structure formed by an inner core and a coating layer is obtained. Under the combined action of the modified material and the special structure, the ferric fluoride-titanium suboxide composite anode material obtained by the invention can still keep better circulation stability and capacity retention rate under higher voltage, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to an iron fluoride-titanium suboxide composite anode material and a preparation method and application thereof.
Background
With the rapid development of new energy automobiles, the lithium ion battery industry has entered a rapid development stage. The key materials influencing the performance of the lithium ion battery mainly comprise a positive electrode material, a negative electrode material, electrolyte and the like. The positive electrode material is a main factor which currently limits the performance of the battery and also a main factor which accounts for the higher cost of the lithium ion battery, and is close to 40%. At present, the anode material mainly comprises lithium cobaltate, lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate ternary material, lithium manganate, lithium iron phosphate and the like, but with the rapid development of new energy automobiles, the demand on the anode material is gradually increased, and elements such as nickel, cobalt and the like also face the problems of limited resources, high price and the like.
The ferric fluoride as a novel conversion type lithium ion battery anode material can store energy by utilizing the chemical conversion reaction between the whole oxidation state of iron and lithium ions, and has high theoretical specific capacity along with the transfer of three electrons. However, since the metal fluoride has a large energy band gap and poor conductivity, further modification is required.
CN103855389A discloses an iron trifluoride/carbon composite material, a preparation method and an application thereof, wherein iron fluoride is modified by carbon, and the composite material comprises 50-90 wt% of iron trifluoride and 10-50 wt% of a carbon material. CN105958040A provides an iron trifluoride composite material, which utilizes a multi-component conductive polymer doped and compounded on iron trifluoride to modify the iron trifluoride, wherein the conductive polymer is two or more of polyaniline, polyurethane, polypyrrole and polythiophene. CN107591524A discloses a preparation method of a graphene-ferric fluoride composite positive electrode material, which is to compound a ferric fluoride material with a silicon-doped graphene material having good conductivity and stability after cobalt doping modification. CN106025182A discloses a titanium-chromium doped ferric fluoride-carbon nano composite anode material and a preparation method thereof, wherein a ferric fluoride precursor is formed after doping titanium ions and chromium ions, and then the ferric fluoride precursor is coated by a carbon-containing conductive material. CN106099074A discloses a preparation method of titanium-doped ferric fluoride anode material, and the general formula of the material is Fe1-xTixF3·0.33H2O/C, x is more than or equal to 0.01 and less than or equal to 0.50. CN107146881A discloses a modified lithium nickel manganese oxide positive electrode composite material, including lithium nickel manganese oxide particles, cladding in the iron fluoride layer on the surface of lithium nickel manganese oxide particles and cladding in the graphite alkene layer on the iron fluoride layer.
In addition to improving the performance of ferric fluoride by doping, the structure is also an important factor affecting its performance. Therefore, how to further perform doping modification on the ferric fluoride and design a proper structure is to solve the problem of poor conductivity of the ferric fluoride in the prior art, and meanwhile, the ferric fluoride obtains more excellent performance, which becomes the direction of efforts of current researchers.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide an iron fluoride-titanium suboxide composite positive electrode material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an iron fluoride-titanium suboxide composite positive electrode material, which is a spherical structure and comprises an inner core and a coating layer, wherein the inner core is iron fluoride and titanium suboxide, and the coating layer is a carbon material.
The invention selects titanium suboxide and carbon material to modify ferric fluoride. Wherein, titanium oxide (T)4O7) The conductive coating has the advantages of ultrahigh conductivity, good electrochemical stability and corrosion resistance and the like; the carbon material has strong conductivity, large specific surface area and certain flexibility, and can buffer the volume change of the material. The titanium suboxide and the carbon material are jointly used for modifying the ferric fluoride particles in a spray drying mode to form the composition of point contact inside a bulk phase and surface contact outside the bulk phase, and a multi-level spherical structure formed by the inner core and the coating layer is obtained. Under the combined action of the modified material and the special structure, the ferric fluoride-titanium suboxide composite cathode material obtained by the invention can improve the thermal stability, the cycle performance and the multiplying power of a battery material.
According to the invention, the content of titanium monoxide in the composite cathode material is 1-15% by mass percentage, and may be 1%, 3%, 5%, 8%, 10%, 13% or 15%, for example, and the specific values between the above values are limited by space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the content of the carbon material in the composite cathode material is 1-40% by mass percentage, and may be, for example, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40%, and the specific values between the above values are limited by space and for the sake of brevity, and are not exhaustive.
According to the mass percentage, the sum of the ferric fluoride, the titanium dioxide and the carbon material in the composite cathode material is 100%.
According to the present invention, the particle size of the composite cathode material is 1-20 μm, for example, 1 μm, 3 μm, 5 μm, 8 μm, 10 μm, 13 μm, 15 μm, 18 μm or 20 μm, and the specific values therebetween are not exhaustive for the sake of brevity and simplicity.
According to the invention, the iron fluoride and the titanium suboxide in the inner core are present in the form of a composite and separate particles, meaning iron fluoride particles and titanium suboxide particles, respectively, which are only in contact with the carbon material.
According to the invention, the structural formula of the iron fluoride and titanium suboxide compound is FeF3/T4O7The particle size of the complex is 0.9-9 μm, and may be, for example, 0.9 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm or 9 μm, and the specific values therebetween are not intended to be exhaustive for reasons of brevity and conciseness.
According to the invention, the particle size of the iron fluoride particles is 0.5-5 μm, and may be, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm or 5 μm, and the values between the above values are not exhaustive for reasons of space and simplicity.
According to the invention, the titanium suboxide particles have a particle size of 0.5 to 5 μm, which may be, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm or 5 μm, and the values between these values are not exhaustive for reasons of space and simplicity.
In a second aspect, the present invention provides a method for preparing a composite positive electrode material as described in the first aspect, the method comprising the steps of:
(1) dispersing ferric fluoride and titanium dioxide in a solvent according to the formula amount, and then adding a carbon source to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) to obtain the composite cathode material.
According to the present invention, the solvent in step (1) is any one or a combination of at least two of water, ethanol, acetone, propanol, isopropanol, isobutanol, methanol, n-butanol, ethylene glycol or chloroform, for example, any one of water, ethanol, acetone, propanol, isopropanol, isobutanol, methanol, n-butanol, ethylene glycol or chloroform, and a typical but non-limiting combination is: water and ethanol, acetone and propanol, isopropanol and isobutanol, methanol and n-butanol, ethylene glycol and chloroform, and the like.
According to the invention, the mass ratio of the sum of the mass of the iron fluoride and the titanium dioxide in the step (1) to the solvent is 1 (5-100), and can be, for example, 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90 or 1:100, and the specific values between the above values are limited to space and for the sake of brevity, and the invention is not exhaustive.
According to the invention, the carbon source in step (1) is any one or a combination of at least two of glucose, sucrose, cellulose, polyethylene glycol, polyvinyl alcohol, soluble starch, single crystal sugar, polycrystalline sugar candy, fructose, citric acid, phenolic resin, vinyl pyrrolidone, epoxy resin, polyalditol, polyvinylidene fluoride, polyvinyl chloride, urea resin, polymethacrylate or furan resin, such as any one of glucose, sucrose, cellulose, polyethylene glycol, polyvinyl alcohol, soluble starch, single crystal sugar, polycrystalline sugar candy, fructose, citric acid, phenolic resin, vinyl pyrrolidone, epoxy resin, polyalditol, polyvinylidene fluoride, polyvinyl chloride, urea resin, polymethacrylate or furan resin, and a typical but non-limiting combination is as follows: glucose and sucrose, polyethylene glycol and polyvinyl alcohol, soluble starch and single crystal rock sugar, polycrystalline rock sugar and fructose, phenolic resin and epoxy resin, polyvinylidene fluoride and polyvinyl chloride, urea-formaldehyde resin, polymethacrylate and the like.
According to the present invention, the temperature of the spray drying in step (2) is 150-.
In a third aspect, the invention provides a use of the composite positive electrode material according to the first aspect, wherein the composite positive electrode material is applied to a lithium ion battery.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the invention, titanium dioxide and a carbon source are utilized to modify ferric fluoride together, a multi-level spherical structure is constructed, and the composition of point contact type inside a bulk phase and external surface contact type is formed, so that the overall conductivity and structural stability of the material can be improved, and the cycle performance and rate capability of the material are improved.
(2) The titanium dioxide selected by the invention has the advantages of high conductivity, good electrochemical stability and corrosion resistance, and the like, and forms a good matching effect with the carbon material, so that the electronic conductivity of the ferric fluoride can be effectively improved, the rate capability of the material is improved, the occurrence of side reactions is reduced, the chemical stability of the material is improved, and the obtained anode material can still keep good cycle stability and capacity retention rate under high voltage.
(3) According to the invention, the carbon source is coated on the surface of the compound particles in a spray drying manner, and the prepared product has high uniformity and good consistency.
Drawings
FIG. 1 is a schematic structural diagram of an iron fluoride-titanium suboxide composite positive electrode material prepared in example 1 of the present invention; wherein, 1-carbon material, 2-ferric fluoride particles, 3-titanium oxide particles, 4-FeF3/T4O7。
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
(1) Dispersing 20g of ferric fluoride and 2g of titanium dioxide in 200g of water, and then adding a certain amount of sucrose to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) at 250 ℃ to obtain the composite cathode material, wherein the carbon content in the material is 20 wt%.
As shown in figure 1, the obtained material is a multilayer spherical structure formed by wrapping a coating layer on an inner core, wherein the inner core is a composite formed by ferric fluoride and titanium dioxide and independent ferric fluoride particles and titanium dioxide particles.
The obtained material is used as a lithium ion battery anode material for electrochemical performance test, and the pole piece ratio is that the composite material: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2-4.5V and the current density of 50mA/g, the first cyclic discharge specific capacity is 215mAh/g, and the capacity retention rate of 200 cycles is 92%.
Example 2
(1) Dispersing 2g of ferric fluoride and 0.1g of titanium dioxide in 200g of alcohol, and then adding a certain amount of polyethylene glycol to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) at the temperature of 150 ℃ to obtain the composite cathode material, wherein the carbon content in the material is 40 wt%.
The obtained material is used as a lithium ion battery anode material for electrochemical performance test, and the pole piece ratio is that the composite material: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2-4.5V and the current density of 50mA/g, the first cyclic discharge specific capacity is 193mAh/g, and the capacity retention rate is 91% after 200 cycles.
Example 3
(1) Dispersing 0.5g of ferric fluoride and 0.05g of titanium monoxide in 5g of n-butanol, and then adding a certain amount of citric acid to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) at the temperature of 200 ℃ to obtain the composite cathode material, wherein the carbon content in the material is 10 wt%.
The obtained material is used as a lithium ion battery anode material for electrochemical performance test, and the pole piece ratio is that the composite material: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2-4.5V and the current density of 50mA/g, the first cyclic discharge specific capacity is 185mAh/g, and the capacity retention rate is 89% after 200 cycles.
Example 4
(1) Dispersing 400g of ferric fluoride and 10g of titanium dioxide in 4000g of ethylene glycol, and then adding a certain amount of epoxy resin to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) at the temperature of 210 ℃ to obtain the composite cathode material, wherein the carbon content in the material is 5 wt%.
The obtained material is used as a lithium ion battery anode material for electrochemical performance test, and the pole piece ratio is that the composite material: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2-4.5V and the current density of 50mA/g, the first cyclic discharge specific capacity is 198mAh/g, and the capacity retention rate is 91% after 200 cycles.
Example 5
(1) Dispersing 40g of ferric fluoride and 6g of titanium dioxide in 400g of propanol, and then adding a certain amount of polyalditol to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) at 250 ℃ to obtain the composite cathode material, wherein the carbon content in the material is 30 wt%.
The obtained material is used as a lithium ion battery anode material for electrochemical performance test, and the pole piece ratio is that the composite material: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2-4.5V and the current density of 50mA/g, the first cyclic discharge specific capacity is 202mAh/g, and the capacity retention rate is 90% after 200 cycles.
Example 6
(1) Dispersing 50g of ferric fluoride and 3g of titanium dioxide in 1000g of chloroform, and then adding a certain amount of soluble starch to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) at the temperature of 150 ℃ to obtain the composite cathode material, wherein the carbon content in the material is 10 wt%.
The obtained material is used as a lithium ion battery anode material for electrochemical performance test, and the pole piece ratio is that the composite material: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2-4.5V and the current density of 50mA/g, the first cyclic discharge specific capacity is 195mAh/g, and the capacity retention rate is 91 percent after 200 cycles.
Comparative example 1
(1) Dispersing 20g of ferric fluoride in 200g of water, and then adding a certain amount of sucrose to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) at the temperature of 250 ℃ to obtain a composite material, wherein the carbon content in the material is 20 wt%.
The obtained material is used as a lithium ion battery anode material for electrochemical performance test, and the pole piece ratio is that the composite material: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2-4.5V and the current density of 50mA/g, the first cyclic discharge specific capacity is 210mAh/g, and the capacity retention rate of 200 cycles is 73%.
Comparative example 2
(1) Dispersing 20g of ferric fluoride and 2g of titanium dioxide in 200g of water to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) at 250 ℃ to obtain the composite cathode material.
The obtained material is used as a lithium ion battery anode material for electrochemical performance test, and the pole piece ratio is that the composite material: acetylene black: PVDF 80:10: 10. And preparing the CR2025 button cell by taking a lithium sheet as a reference electrode. Under the voltage window of 2-4.5V and the current density of 50mA/g, the first cyclic discharge specific capacity is 215mAh/g, and the capacity retention rate of 200 cycles is 45%.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. The composite positive electrode material is characterized by being of a spherical structure and comprising an inner core and a coating layer, wherein the inner core is made of ferric fluoride and titanium suboxide, and the coating layer is made of a carbon material;
the iron fluoride and the titanium suboxide exist in the form of a compound, iron fluoride particles and titanium suboxide particles in the inner core;
the ferric fluoride-titanium dioxide composite positive electrode material is prepared by adopting the following method, and the method comprises the following steps:
(1) dispersing ferric fluoride and titanium dioxide in a solvent according to the formula amount, and then adding a carbon source to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) to obtain the composite cathode material.
2. The composite positive electrode material according to claim 1, wherein the content of titanium monoxide in the composite positive electrode material is 1 to 15% by mass.
3. The composite positive electrode material according to claim 1, wherein the content of the carbon material in the composite positive electrode material is 1 to 40% by mass.
4. The composite positive electrode material according to claim 1, wherein the particle size of the composite positive electrode material is 1 to 20 μm.
5. The composite positive electrode material according to claim 1, wherein the iron fluoride and titanium suboxide composite has a structural formula of FeF3/T4O7The particle size of the compound is 0.9-9 μm.
6. The composite positive electrode material according to claim 1, wherein the iron fluoride particles have a particle size of 0.5 to 5 μm.
7. The composite positive electrode material according to claim 1, wherein the titanium suboxide particles have a particle diameter of 0.5 to 5 μm.
8. The method for preparing a composite positive electrode material according to any one of claims 1 to 7, characterized in that the method comprises the steps of:
(1) dispersing ferric fluoride and titanium dioxide in a solvent according to the formula amount, and then adding a carbon source to obtain a composite solution;
(2) and (2) carrying out spray drying on the composite solution obtained in the step (1) to obtain the composite cathode material.
9. The method of claim 8, wherein the solvent in step (1) is any one or a combination of at least two of water, ethanol, acetone, propanol, isopropanol, isobutanol, methanol, n-butanol, ethylene glycol, and chloroform.
10. The method according to claim 8, wherein the mass ratio of the sum of the mass of the ferric fluoride and the titanium oxide to the solvent in the step (1) is 1 (5-100).
11. The method of claim 8, wherein the carbon source in step (1) is any one of or a combination of at least two of glucose, sucrose, cellulose, polyethylene glycol, polyvinyl alcohol, soluble starch, single crystal sugar, polycrystalline sugar, fructose, citric acid, phenolic resin, vinyl pyrrolidone, epoxy resin, polyalditol, polyvinylidene fluoride, polyvinyl chloride, urea formaldehyde resin, polymethacrylate, or furan resin.
12. The method as claimed in claim 8, wherein the temperature of the spray drying in the step (2) is 150 ℃ to 250 ℃.
13. Use of a composite positive electrode material according to any one of claims 1 to 7, wherein the composite positive electrode material is used in a lithium ion battery.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496704A (en) * | 2011-12-08 | 2012-06-13 | 中信国安盟固利电源技术有限公司 | Lithium titanate/titanium black anode material and preparation method thereof |
| CN102623707A (en) * | 2012-04-02 | 2012-08-01 | 湘潭大学 | Cobalt-doped carbon-coated ferric fluoride anode material and preparation method thereof |
| CN106025182A (en) * | 2016-08-03 | 2016-10-12 | 广东工业大学 | Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof |
| CN106532003A (en) * | 2016-12-07 | 2017-03-22 | 西南石油大学 | Ti4O7-coated modified lithium titanate composite material and preparation method thereof |
| CN107359321A (en) * | 2017-06-09 | 2017-11-17 | 深圳启辰新能源科技有限公司 | Lithium sulfur battery anode material of the nitrogen-doped carbon of spherical structure/titanium oxide bivalve cladding titanium oxide/sulphur and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102496704A (en) * | 2011-12-08 | 2012-06-13 | 中信国安盟固利电源技术有限公司 | Lithium titanate/titanium black anode material and preparation method thereof |
| CN102623707A (en) * | 2012-04-02 | 2012-08-01 | 湘潭大学 | Cobalt-doped carbon-coated ferric fluoride anode material and preparation method thereof |
| CN106025182A (en) * | 2016-08-03 | 2016-10-12 | 广东工业大学 | Titanium and chromium doped iron fluoride-carbon nanometer composite positive electrode material, and preparation method and application thereof |
| CN106532003A (en) * | 2016-12-07 | 2017-03-22 | 西南石油大学 | Ti4O7-coated modified lithium titanate composite material and preparation method thereof |
| CN107359321A (en) * | 2017-06-09 | 2017-11-17 | 深圳启辰新能源科技有限公司 | Lithium sulfur battery anode material of the nitrogen-doped carbon of spherical structure/titanium oxide bivalve cladding titanium oxide/sulphur and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Iron fluoride microspheres by titanium dioxide surface modification as high capacity cathode of Li-ion batteries;Rui Zhang等;《Journal of Alloys and Compounds》;20170520;第719卷;第331-340页 * |
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Address after: 065001 No. 1 Fenghua Road, Science and Technology Valley, Langfang Development Zone, Langfang City, Hebei Province Patentee after: Langfang green industry technology service center Patentee after: Institute of Process Engineering, Chinese Academy of Sciences Address before: 065001 No. 1 Fenghua Road, Science and Technology Valley, Langfang Development Zone, Langfang City, Hebei Province Patentee before: LANGFANG INSTITUTE OF PROCESS ENGINEERING, CAS Patentee before: Institute of Process Engineering, Chinese Academy of Sciences |