CN113321243A - Lithium ion battery anode material with flower-shaped structure, preparation method and application - Google Patents
Lithium ion battery anode material with flower-shaped structure, preparation method and application Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000004729 solvothermal method Methods 0.000 claims abstract description 8
- 239000010406 cathode material Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000007774 positive electrode material Substances 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000906 Bronze Inorganic materials 0.000 claims description 6
- 239000010974 bronze Substances 0.000 claims description 6
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention discloses a lithium ion battery anode material with a flower-shaped structure, which is obtained by adopting a solvothermal synthesis method through the following raw materials: fe (NO)3)3·9H2O; absolute ethyl alcohol; an ionic liquid; an initiator; wherein the absolute ethanol is Fe (NO) in mass3)3·9H220 to 40 times the mass of O; the mass of the ionic liquid is Fe (NO)3)3·9H210 to 15 times the mass of O; the initiator mass is Fe (NO)3)3·9H20.5 to 1 times of the mass of O; the invention also discloses a preparation method and application of the cathode material; the nanometer material with flower-like structure is applied to lithium ionsThe battery anode is fully contacted with the electrolyte, and the battery performance is favorably improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery anode material with a flower-shaped structure, a preparation method and application.
Background
The performance of the positive electrode material, which is used as one side for providing a lithium source in the lithium ion battery, has a decisive role in the lithium ion battery, and the liquid absorption performance and the stability of the positive electrode material influence the cycle life of the lithium ion battery. In order to further prolong the cycle life of the lithium ion battery, a positive electrode material with good liquid absorption performance and good stability needs to be developed.
The ferric fluoride as a new 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, has high theoretical specific capacity along with the transfer of three electrons, but has uncontrollable manufacturing process and is not optimistic to be applied to lithium ion batteries.
Disclosure of Invention
The invention aims to provide a lithium ion battery anode material with a flower-like structure.
In order to solve the technical problem, the technical scheme of the invention is as follows: a lithium ion battery anode material with a flower-like structure is obtained by adopting a solvothermal synthesis method from the following raw materials:
Fe(NO3)3·9H2o; absolute ethyl alcohol; an ionic liquid; an initiator;
wherein the absolute ethanol is Fe (NO) in mass3)3·9H 220 to 40 times the mass of O;
the mass of the ionic liquid is Fe (NO)3)3·9H 210 to 15 times the mass of O;
the initiator mass is Fe (NO)3)3·9H20.5 to 1 times the mass of O.
Preferably, the mass of the absolute ethyl alcohol is Fe (NO)3)3·9H225 times the mass of O. In the invention, absolute ethyl alcohol is used as a solvent to fully dissolve Fe (NO)3)3·9H2And O, ensuring that the reaction is fully carried out.
Preferably the mass of the ionic liquid is Fe (NO)3)3·9H212 times the mass of O. The invention adjusts the dosage of the ionic liquid inThe full reaction is ensured, the system density of the reaction is also ensured, and the reaction speed is ensured. Preferably, the initiator is metallic titanium or platinum. The initiator initiates the ionic liquid and ferric nitrate to carry out oxidation reduction in the reaction kettle, and the metal titanium or platinum can initiate the reaction, and the effects of the ionic liquid and the ferric nitrate are the same.
Preferably, the ionic liquid is [ Bmim ] BF 4. In the invention, absolute ethyl alcohol and [ Bmim ] BF4 ionic liquid are used as mixed solvents, and [ Bmim ] BF4 is used as a fluorine source of a target product.
The invention also provides a preparation method of the lithium ion battery cathode material with the flower-like structure.
In order to solve the technical problem, the technical scheme of the invention is as follows: a preparation method of a lithium ion battery anode material comprises the following steps:
step one, taking Fe (NO)3)3·9H2Dissolving O in absolute ethyl alcohol, and stirring until Fe (NO) is obtained3)3·9H2Completely dissolving the O;
step two, slowly adding the ionic liquid into the solution obtained in the step one, and continuously stirring until the mixed solution is gradually changed from orange to clear pale yellow solution;
step three, adding the solution obtained in the step two into a reaction kettle, quickly adding an initiator, sealing the reaction kettle, and carrying out solvothermal synthesis;
and step four, after the reaction is finished, repeatedly cleaning the powder at the bottom of the collecting kettle by using acetone and ethanol, and then carrying out vacuum drying at the temperature of 80 ℃ to obtain a target product.
In the second step of the invention, the ionic liquid is slowly added to prevent the ionic liquid from locally reacting with ferric nitrate to generate byproducts due to overlarge local concentration. With the addition of the ionic liquid, ferric nitrate is contacted with the ionic liquid, and part of iron ions are combined with the ionic liquid to form a polymer, so that the next solvothermal synthesis is carried out.
In the third step of the invention, the volume of the reaction kettle is 3 to 5 times of the volume of the mixed solution added into the reaction kettle; the volume of the reaction kettle is moderate, the volume is too large, the reaction is incomplete, the volume of the reaction kettle is too small, the internal temperature is too high and unsafe when the reaction is carried out, and preferably 4 times of the volume of the solvent in the reaction kettle and the mixed liquid in the reaction kettle.
Step four of the invention uses acetone and ethanol for repeated washing, and then vacuum drying is carried out at 80 ℃.
The preferable technological conditions of the solvothermal synthesis in the third step are as follows:
the reaction temperature is 100 ℃ to 120 ℃;
the reaction time is 8 to 16 hours.
The preferable technological conditions of the solvothermal synthesis in the third step are as follows:
the reaction temperature is 120 ℃;
the reaction time was 10 hours.
The solvent thermal synthesis time is 10h and the temperature is 120 ℃ preferably.
Preferably, the target product is FeF of hexagonal tungsten bronze phase3·0.33H2And O. The target material obtained by the invention is in a flower-shaped nano structure, and the target material is applied to the lithium ion battery to obviously improve the cycle performance of the battery.
The invention aims to provide application of a lithium ion battery anode material with a flower-like structure.
In order to solve the technical problem, the technical scheme of the invention is as follows: the lithium ion battery anode material prepared by the invention is applied to a lithium ion battery, and the lithium ion battery is a liquid battery or a solid battery.
The cathode material of the lithium ion battery is one or more of graphite or silicon-carbon materials and the like which can receive lithium ion materials.
By adopting the technical scheme, the invention has the beneficial effects that:
the invention uses absolute ethyl alcohol and ionic liquid as mixed solvent to carry out solvent thermal synthesis reaction under the action of initiatorFeF of nano flower-shaped hexagonal tungsten bronze phase is prepared3·0.33H2Compared with nanoparticles, the flower-like structure of the nanoparticles has more pores, and the application of the nanoparticles as a lithium ion battery anode material can help lithium ions to be freely desorbed and prolong the cycle life;
meanwhile, when the micro-nano material with the flower-shaped structure is used as the anode of the lithium ion battery, the structural advantages of the material are fully exerted, the tiny size of the nano construction unit can effectively shorten the diffusion distance of electrons and lithium ions, the high specific surface area can ensure that the electrode is fully contacted with electrolyte, and active substances are fully contacted with the electrolyte, so that more active reaction sites and higher capacity are provided; the porous structure is beneficial to the transmission and diffusion of the electrolyte;
the positive electrode material provided by the invention has the advantages that the flower-shaped nano construction units are firmly combined to ensure the stability of the material structure; compared with nano particles, the flower-shaped structure electrode is not easy to agglomerate and pulverize, and the active material of the positive plate has good flexibility and high cycling stability.
Thereby achieving the above object of the present invention.
Drawings
FIG. 1 shows FeF of hexagonal tungsten bronze phase according to the invention3·0.33H2An XRD pattern of O;
FIG. 2 shows FeF prepared by the present invention3·0.33H2SEM picture of O;
FIG. 3 is a graph of the cycle performance of lithium ion batteries obtained in examples 1 to 3 of the present invention; at 25 ℃, 0.5C charge, 1C discharge cycle.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
The embodiment discloses a lithium ion battery anode material with a flower-shaped structure and a preparation method thereof, and the preparation method comprises the following specific steps:
step one, taking 2g of Fe (NO)3)3·9H2Dissolving O in 40mL of absolute ethanol, stirring for 30min until the completion of Fe (NO3) 3.9H 2OFully dissolving;
and step two, slowly adding 20mL of [ Bmim ] BF4 into the mixed solution in the step one, continuing stirring for 30min, and gradually changing the mixed solution from orange to clear pale yellow solution.
And step three, adding the mixed solution into a 300mL polytetrafluoroethylene reaction kettle, quickly putting 1g of initiator titanium into the reaction kettle, sealing the reaction kettle, and reacting for 8 hours in a blast drying oven at 100 ℃.
And step four, after the reaction is finished, taking out the array anode material, repeatedly cleaning the array anode material by using acetone and ethanol, and then carrying out vacuum drying at the temperature of 80 ℃ for later use to obtain a product.
Example 2
The embodiment discloses a lithium ion battery anode material with a flower-shaped structure and a preparation method thereof, and the preparation method comprises the following specific steps:
step one, taking 2g of Fe (NO)3)3·9H2Dissolving O in 60mL of absolute ethanol, stirring for 30min until Fe (NO) is obtained3)3·9H2Completely dissolving the O;
and step two, slowly adding 25mL of [ Bmim ] BF4 into the mixed solution in the step one, continuing stirring for 30min, and gradually changing the mixed solution from orange to clear pale yellow solution.
And step three, adding the mixed solution into a 300mL polytetrafluoroethylene reaction kettle, quickly putting 1.5g of initiator platinum into the reaction kettle, sealing the reaction kettle, and reacting for 9 hours in a forced air drying oven at 110 ℃.
And step four, after the reaction is finished, taking out the array anode material, repeatedly cleaning the array anode material by using acetone and ethanol, and then carrying out vacuum drying at the temperature of 80 ℃ for later use to obtain a product.
Example 3
The embodiment discloses a lithium ion battery anode material with a flower-shaped structure and a preparation method thereof, and the preparation method comprises the following specific steps:
step one, taking 2gFe (NO)3)3·9H2Dissolving O in 80mL of absolute ethanol, stirring for 30min until Fe (NO) is obtained3)3·9H2Completely dissolving the O;
and step two, slowly adding 30mL of [ Bmim ] BF4 into the mixed solution in the step one, continuing stirring for 30min, and gradually changing the mixed solution from orange to clear pale yellow solution.
And step three, adding the mixed solution into a 200mL polytetrafluoroethylene reaction kettle, quickly putting 2g of initiator platinum into the reaction kettle, sealing the reaction kettle, and reacting in a blast drying oven at 120 ℃ for 10 hours.
And step four, after the reaction is finished, taking out the array anode material, repeatedly cleaning the array anode material by using acetone and ethanol, and then carrying out vacuum drying at the temperature of 80 ℃ for later use to obtain a product.
FeF, the target products of comparative example and examples 1 to 3, were applied to a battery system3·0.33H2O is used as a positive electrode material, matched with negative electrode graphite, electrolyte and an isolating membrane, the materials are prepared into a battery with extremely low water oxygen content (H)2O<0.1ppm，O2<1ppm) was charged with argon and the assembly was carried out in a glove box filled with argon. During assembly, a positive pole piece is sequentially placed in a positive shell, then an isolating membrane and a negative pole are placed, electrolyte is dripped, finally, foamed nickel is placed to ensure good conductive contact inside the electrode, a negative shell is covered, and battery packaging is carried out by using a button battery manual sealing machine.
And (3) performance testing:
1. testing the liquid absorption performance: after the positive electrode piece of 10cm x 10cm was immersed in the electrolyte for 12 hours, the liquid absorption was measured, and the specific test data are shown in table 1.
2. And (3) testing the cycle performance: the target materials prepared in examples 1 to 3 were used to prepare batteries, which were placed in a Xinwei test cabinet for cycle performance testing for 50 cycles, and the cycle results are shown in FIG. 3.
Table 1 examples 1 to 3 FeF was prepared3·0.33H2Test data of imbibition performance of positive plate made of O
| Group of | Liquid absorption amount/g |
| Comparative example | 0.1g |
| Example 1 | 0.4g |
| Example 2 | 0.6g |
| Example 3 | 0.5g |
The invention prepares the FeF of the nanometer flower-shaped hexagonal tungsten bronze phase by taking absolute ethyl alcohol and ionic liquid as a mixed solvent to carry out solvothermal synthesis reaction under the action of an initiator3·0.33H2O, as shown in FIGS. 1 and 2, from the XRD data patterns, between 20 and 30, a hexagonal tungsten bronze phase FeF appears3·0.33H2The characteristic diffraction peak of O proves that the product is FeF3·0.33H2O; from FIG. 2, it can be seen that FeF prepared by the present invention3·0.33H2O is a flower-shaped structure, and the layers are clear and are arranged orderly.
FeF prepared by the method relative to nano particles3·0.33H2The O flower-shaped structure has more pore channels, and the O flower-shaped structure is applied as a lithium ion battery anode material to help free desorption of lithium ions and prolong the cycle life; meanwhile, when the micro-nano material with the flower-shaped structure is used as the anode of the lithium ion battery, the structural advantages of the material are fully exerted, the tiny size of the nano construction unit can effectively shorten the diffusion distance of electrons and lithium ions, the high specific surface area can ensure that the electrode is fully contacted with electrolyte, and active substances are fully contacted with the electrolyte, so that more active reaction sites and higher capacity are provided; the porous structure is beneficial to the transmission and diffusion of the electrolyte; the positive electrode material of the present invention has a flowerThe firm combination among the nano-structure units ensures the stability of the material structure; compared with nano particles, the flower-shaped structure electrode is not easy to agglomerate and pulverize, and the active material of the positive plate has good flexibility and high cycling stability.
According to imbibition data, the positive pole piece 10cm x 10cm made of the product can absorb 0.6g of electrolyte at most, after the button cell prepared by the product is cycled for 50 weeks, the capacity retention rate is up to 97%, and the imbibition performance and the cycle performance are superior to reported data.
The above embodiments and drawings are not intended to limit the form and style of the present invention, and any suitable changes or modifications thereof by those skilled in the art should be considered as not departing from the scope of the present invention.
Claims (10)
1. The lithium ion battery cathode material with the flower-like structure is characterized in that: the preparation method is characterized by comprising the following steps of:
Fe(NO3)3·9H2o; absolute ethyl alcohol; an ionic liquid; an initiator;
wherein the absolute ethanol is Fe (NO) in mass3)3·9H220 to 40 times the mass of O;
the mass of the ionic liquid is Fe (NO)3)3·9H210 to 15 times the mass of O;
the initiator mass is Fe (NO)3)3·9H20.5 to 1 times the mass of O.
2. The positive electrode material of the lithium ion battery with the flower-like structure as claimed in claim 1, wherein: the absolute ethyl alcohol is Fe (NO) in mass3)3·9H225 times the mass of O.
3. The positive electrode material of the lithium ion battery with the flower-like structure as claimed in claim 1, wherein: the mass of the ionic liquid is Fe (NO)3)3·9H212 times the mass of O.
4. The positive electrode material of the lithium ion battery with the flower-like structure as claimed in claim 1, wherein: the initiator is metallic titanium or platinum.
5. The positive electrode material of the lithium ion battery with the flower-like structure as claimed in claim 1, wherein: the ionic liquid is [ Bmim ] BF 4.
6. A method for preparing the positive electrode material of the lithium ion battery according to any one of claims 1 to 5, wherein:
the method comprises the following steps:
step one, taking Fe (NO)3)3·9H2Dissolving O in absolute ethyl alcohol, and stirring until Fe (NO) is obtained3)3·9H2Completely dissolving the O;
step two, slowly adding the ionic liquid into the solution obtained in the step one, and continuously stirring until the mixed solution is gradually changed from orange to clear pale yellow solution;
step three, putting the solution obtained in the step two into a reaction kettle, adding an initiator, sealing the reaction kettle, and carrying out solvothermal synthesis;
and step four, after the reaction is finished, repeatedly cleaning the powder at the bottom of the collecting kettle by using acetone and ethanol, and then carrying out vacuum drying at the temperature of 80 ℃ to obtain a target product.
7. The method for preparing the positive electrode material of the lithium ion battery according to claim 6, wherein the method comprises the following steps: the process conditions of the solvent thermal synthesis in the step three are as follows:
the reaction temperature is 100 ℃ to 120 ℃;
the reaction time is 8 to 16 hours.
8. The method for preparing the positive electrode material of the lithium ion battery according to claim 6, wherein the method comprises the following steps: the process conditions of the solvent thermal synthesis in the step three are as follows:
the reaction temperature is 120 ℃;
the reaction time was 10 hours.
9. The method for preparing the positive electrode material of the lithium ion battery according to claim 6, wherein the method comprises the following steps: FeF with target product of hexagonal tungsten bronze phase3·0.33H2O。
10. The application of the lithium ion battery cathode material of any one of claims 1 to 5 to a lithium ion battery, wherein:
the lithium ion battery is a liquid battery or a solid battery.
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