CN111883775A - Limiting composite ferric trifluoride positive electrode material, preparation method and application - Google Patents
Limiting composite ferric trifluoride positive electrode material, preparation method and application Download PDFInfo
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- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000007774 positive electrode material Substances 0.000 title abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002608 ionic liquid Substances 0.000 claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- 238000001308 synthesis method Methods 0.000 claims abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 23
- 229910001416 lithium ion Inorganic materials 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 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
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 5
- 239000007784 solid electrolyte Substances 0.000 claims description 5
- 239000010406 cathode material Substances 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 2
- -1 compound ferric trifluoride Chemical class 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000002159 nanocrystal Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002203 sulfidic glass Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 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
- 238000007709 nanocrystallization Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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Abstract
The invention discloses a limiting composite ferric trifluoride positive electrode material, which is FeF synthesized by a liquid phase synthesis method from a carbon material and ferric salt3·0.33H2An O-carbon material; the carbon material is graphene or mesoporous carbon; the invention also discloses a preparation method of the limiting composite ferric trifluoride anode material, which comprises the following steps: firstly, dispersing a carbon material in concentrated nitric acid, refluxing, and carrying out suction filtration on a refluxed solution to obtain a pure carbon material; secondly, purifying the product obtained in the first stepUltrasonically dispersing a net carbon material in absolute ethyl alcohol; thirdly, adding an iron source and ionic liquid into the absolute ethyl alcohol with the uniformly dispersed carbon material obtained in the third step; step four, stirring and reacting the mixture obtained in the step three at a first temperature for a period of time, heating to a second temperature, finishing the reaction at the second temperature, cleaning, and drying to obtain a target product; the invention controls the size of the iron trifluoride crystal in a limiting way and prevents the crystal agglomeration; the synthesis is simple and convenient; is suitable for application.
Description
Technical Field
The invention relates to the technical field of chemical power supplies, in particular to a limiting composite ferric trifluoride anode material, a preparation method and application.
Background
As a practical energy conversion device, a lithium ion battery has been widely applied to various fields of daily life, the energy density of the existing lithium ion battery system is close to a theoretical value, breakthrough development is difficult to achieve, and development of a new lithium ion battery system, especially a new electrode material, has important significance.
The ferric fluoride as a typical representative of the anode material of the new-generation lithium ion battery has the advantages of high theoretical capacity, abundant resources, low cost and the like, and attracts the wide attention of researchers. However, fluorine and iron are bonded through ionic bonds, so that the electronic conductivity of the material is low, and the exertion of the rate capability of the material is greatly restricted, so that the improvement of the electronic conductivity of the iron fluoride is the first problem in the commercialization process of the iron fluoride.
The current modification research on the ferric fluoride material mainly focuses on the following three aspects: firstly, a nanocrystallization means is adopted to control the microstructure and the appearance of the ferric fluoride material, secondly, a composite method is adopted to be compounded with a carbon material with high electronic conductivity, and thirdly, ion doping is carried out, so that the electronic conductivity of the ferric fluoride is fundamentally improved.
Disclosure of Invention
The invention aims to provide a limiting composite ferric trifluoride cathode material, which limits and controls the size of ferric trifluoride crystals and prevents the crystals from agglomerating.
In order to solve the technical problem, the technical scheme of the invention is as follows: a limiting composite ferric trifluoride positive electrode material is FeF synthesized from a carbon material and an iron salt through a liquid phase synthesis method3·0.33H2An O-carbon material;
the carbon material is graphene or mesoporous carbon.
The invention aims to provide a preparation method of a limiting composite ferric trifluoride anode material, the invention limits the crystal growth of ferric trifluoride by utilizing the structure of a carbon material through liquid-phase in-situ synthesis, and the preparation process is simple.
In order to solve the technical problem, the technical scheme of the invention is as follows: a preparation method of a limiting composite ferric trifluoride anode material comprises the following steps:
dispersing a carbon material in concentrated nitric acid, refluxing, and carrying out suction filtration on a refluxed solution to obtain a pure carbon material;
step two, ultrasonically dispersing the pure carbon material prepared in the step one in absolute ethyl alcohol;
step three, adding Fe (NO)3)3·9H2O and [ Bmim ]][BF4]Adding the ionic liquid into the absolute ethyl alcohol with the uniformly dispersed carbon material obtained in the third step;
and step four, stirring the mixture obtained in the step three at the first temperature for reacting for a period of time, heating to a second temperature, finishing the reaction at the second temperature, cleaning, and drying to obtain the powdery ferric fluoride-carbon material.
Preferably step four washes the product with acetone. The purpose of washing with acetone in the invention is to remove the nanoparticles attached to the surface of the carbon material, smoothen the surface of the material and reduce the specific surface area of the material.
Preferably Fe (NO)3)3·9H2The amount of O is 2 to 5 times the amount of the carbon material, [ Bmim ]][BF4]The amount of the substance of the ionic liquid is 20 to 30 times the amount of the substance of the carbon material.
It is preferable that the amount of the anhydrous ethanol substance is 30 to 50 times the amount of the carbon material substance. In the invention, the consumption of the absolute ethyl alcohol is too small, the carbon material cannot be uniformly dispersed, and the consumption is large and is easy to waste.
Preferably the first temperature in step four is in the range of 0 to 5 ℃;
the second temperature is 60 to 80 ℃, and the reaction time at the second temperature is 6 to 10 hours. In the present invention, the first temperature is controlled to 0 to 5 ℃ to make Fe (NO)3)3·9H2O is fully dissolved and is not hydrolyzed into ferric hydroxide, so that the purity of the product is influenced; the second temperature is 60-80 deg.C, the time is 6-10h, the reaction temperature is too high, and Fe (NO)3)3·9H2O is easy to hydrolyze, the reaction temperature is low, and the reaction is incomplete; the reaction time and the reaction temperature are matched with each other, the time is too short, the reaction is insufficient, the time is too long, the time consumption is proper, and the production cost is wasted; more preferably, the second temperature is 60 ℃ and the reaction time is 8 h.
A third object of the present invention is to provide a lithium ion battery which is high voltage and high capacity.
In order to solve the technical problem, the technical scheme of the invention is as follows: a solid state lithium ion battery, a positive electrode, a negative electrode and a solid state electrolyte, wherein the positive electrode comprises the FeF of claim 13·0.33H2An O-carbon material.
Preferably, the positive electrode further comprises sulfide, and the sulfide is one or more of iron sulfide, cobalt sulfide and tungsten sulfide. FeF of the invention3·0.33H2After the O-carbon material is matched with sulfide, the integral gram capacity of the anode material can be improved; the whole anode material has the advantages of high voltage and high gram capacity, and is suitable for being applied to a solid-state battery system.
Further preferred is FeF3·0.33H2The mass ratio of the O-carbon material to the sulfide is 6: 4 to 8: 2. FeF of the above-mentioned ratio3·0.33H2After the O-carbon material and the sulfide are mixed, the gram capacity at 0.5 ℃ is more than 350mAh/g, the voltage is between 1.7 and 4.5V, the high-voltage and high-capacity lithium ion battery has the characteristics of high voltage and high capacity, the cycle performance and the rate performance are excellent, the capacity retention rate is more than 96 percent after the cycle is performed for 50 weeks, and the performance of the lithium ion battery is excellent.
Preferably, the negative electrode is a lithium sheet, which is beneficial to the exertion of excellent performance of the positive electrode material.
By adopting the technical scheme, the invention has the beneficial effects that:
first, FeF in the invention3·0.33H2The O-carbon material, graphene or mesoporous carbon on one hand constructs a conductive network, and on the other hand, the iron trifluoride nanocrystals grow on the pore structure of the graphene or mesoporous carbon, so that the size of the iron fluoride nanocrystals can be controlled, the nanocrystal agglomeration is inhibited, and the tiny iron fluoride nanocrystals are prepared, wherein the smaller the iron fluoride nanocrystals are, the smaller the Li content is, the+The shorter the transmission distance is, the better the rate performance of the material is; the lithium ion battery has excellent electrochemical performance;
secondly, the invention disperses and purifies the carbon material by a liquid phase synthesis preparation method, then an iron source is placed in a mixed system, and FeF is subjected to the reaction of a first temperature and a second temperature3·0.33H2The O nanocrystalline nucleates and grows in and on the pore canal and the surface of the carbon material, the grain size of the crystal is effectively controlled, and the composite anode material with high-quality specific capacity, stable cycle performance and outstanding rate performance is obtained;
and thirdly, the voltage of the lithium ion battery is between 1.7 and 4.5V, the gram capacity of the lithium ion battery at 0.5C is more than 350mAh/g, after the lithium ion battery is circulated for 50 weeks, the capacity retention rate is more than 96 percent, and the lithium ion battery has excellent performance.
Thereby achieving the above object of the present invention.
Drawings
FIG. 1 is an XRD pattern of a composite iron trifluoride cathode material prepared in example 1;
FIG. 2 is an SEM photograph of a composite ferric trifluoride cathode material obtained in example 1.
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
This example synthesizes FeF3·0.33H2The O-graphene composite material comprises the following specific synthetic steps:
step one, dispersing 0.5g of graphene in 30mL of concentrated nitric acid, refluxing for 1h at the temperature of 25 ℃, and filtering the refluxed solution to obtain a pure graphene substance;
step two, ultrasonically dispersing the graphene with the impurities removed in 15mL of absolute ethyl alcohol;
step three, adding 1gFe (NO)3)3·9H2O and 10mL [ Bmim ]][BF4]Adding the ionic liquid into anhydrous ethanol with uniformly dispersed graphene, stirring and reacting for 24h at 0 ℃, then heating to 60 ℃, and reacting for 8h at high temperature to enable FeF3·0.33H2The O nanocrystals will nucleate and grow in the graphene channels and on the surface, resulting in the product, as shown in fig. 2.
Step four, after the reaction is finished, washing the product for three times by using acetone to remove the nano particles attached to the surface of the graphene, centrifuging the solution to obtain a solid product, and drying to obtain powdered FeF3·0.33H2O-graphene. As can be seen from FIGS. 1 and 2, all diffraction peaks of the sample can be assigned to FeF of orthorhombic system3·0.33H2And O. The diffraction peak intensity is relatively low, which may be related to a lower crystallization temperature. The broadening phenomenon appears on each diffraction peak, which indicates that FeF is formed3·0.33H2O smaller sized nanoparticles.
FeF is mixed3·0.33H2O-graphene and iron sulfide are mixed according to the mass ratio of 7: 3, compounding into a positive electrode material, matching with a dispersing agent, a conductive agent and a binder to prepare positive electrode slurry, uniformly coating the positive electrode slurry on a foil, and drying, cold pressing and flaking to obtain the positive electrode piece. The oxygen content of the battery in water is very low (H)2O<0.1ppm，O2<1ppm) was filled with argon and assembled in a glove box. During assembly, a positive pole piece is sequentially placed in a positive shell, then a metal lithium piece coated with sulfide solid electrolyte is placed, 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. The lithium ion battery is laminated with a negative pole piece and a solid electrolyte to prepare a solid-state electricity-saving battery, wherein the negative pole is made of lithium metal; solid electrolyte separatorWith sulfide solid electrolyte: li2S-P2S5-P2S3。
The solid-state lithium ion battery prepared in the embodiment is subjected to electrochemical performance test, and the specific test method is as follows:
cycle testing
In an environment of 25 ℃, charging the battery cell to 4.5V at a constant current of 1C, keeping the voltage constant to 0.05C, standing for 5min, discharging the 1C to 1.7V, standing for 5min, then charging to 4.5V at the constant current of 1C, keeping the voltage constant to 0.05C, standing for 5min, discharging the 1C to 1.7V, standing for 5min, circularly charging and discharging, recording the percentage of the residual capacity of the battery cell after 50 cycles, and calculating the residual gram capacity.
Multiplying power test
After the battery is fully charged at 25 ℃, discharging is carried out under different multiplying factors respectively, the discharging capacity is recorded, and the gram capacity of the anode material is calculated by using the capacity and the coating mass of the anode: capacity/coating mass.
The electrochemical performance test data of the battery prepared in this example are shown in tables 1 and 2.
Example 2
This example synthesizes FeF3·0.33H2The O-mesoporous carbon composite material comprises the following specific synthetic steps:
step one, dispersing 0.5g of mesoporous carbon in 20mL of concentrated nitric acid, refluxing for 1h at the temperature of 25 ℃, and filtering the refluxed solution to obtain a pure mesoporous carbon substance;
step two, ultrasonically dispersing the mesoporous carbon with impurities removed in 20mL of absolute ethyl alcohol;
step three, adding 2gFe (NO)3)3·9H2O and 13mL [ Bmim ]][BF4]Adding the ionic liquid into absolute ethyl alcohol with uniformly dispersed mesoporous carbon;
step four, stirring and reacting for 24 hours at the temperature of 5 ℃, then heating to 70 ℃, reacting for 6 hours at high temperature, and FeF3·0.33H2And (4) nucleating and growing the O nanocrystals on the mesoporous carbon pore canals and the surfaces to obtain the product. After the reaction is finished, the product is washed for three times by acetone to remove the nano particles attached to the surface of the mesoporous carbon, the solution is centrifuged to obtain a solid product,drying to obtain powdered FeF3·0.33H2O-mesoporous carbon;
FeF is mixed3·0.33H2The ratio of the O-mesoporous carbon to the iron sulfide is 8: 2 compounding into a positive electrode material, matching with a dispersing agent, a conductive agent and a binder to prepare a positive electrode slurry, uniformly coating the slurry on a foil, drying, cold pressing and flaking to obtain a positive electrode piece, and laminating the positive electrode piece, a negative electrode piece and a solid electrolyte to prepare a solid-state electricity-buckling battery;
the specific electrochemical test mode of this example is the same as that of example 1, and the specific test data are shown in tables 1 and 2.
Example 3
This example synthesizes FeF3·0.33H2The O-mesoporous carbon composite material comprises the following specific synthetic steps:
step one, dispersing 0.5g of mesoporous carbon in 30mL of concentrated nitric acid, refluxing for 1h at the temperature of 25 ℃, and filtering the refluxed solution to obtain a pure mesoporous carbon substance;
step two, ultrasonically dispersing the mesoporous carbon with impurities removed in 30mL of absolute ethyl alcohol;
step three, adding 3gFe (NO)3)3·9H2O and 15mL [ Bmim ]][BF4]Adding the ionic liquid into absolute ethyl alcohol with uniformly dispersed mesoporous carbon;
step four, stirring and reacting for 24 hours at the temperature of 5 ℃, then heating to 80 ℃, reacting for 10 hours at high temperature, and FeF3·0.33H2And (4) nucleating and growing the O nanocrystals on the mesoporous carbon pore canals and the surfaces to obtain the product. After the reaction is finished, washing the product for three times by using acetone to remove the nano particles attached to the surface of the mesoporous carbon, centrifuging the solution to obtain a solid product, and drying to obtain powdered FeF3·0.33H2O-mesoporous carbon;
FeF is mixed3·0.33H2O-mesoporous carbon and iron sulfide according to the mass ratio of 6: 4, compounding an anode material, matching with a dispersing agent, a conductive agent and a binder to prepare anode slurry, uniformly coating the anode slurry on a foil, drying, cold pressing and flaking to obtain an anode piece, and laminating the anode piece, a cathode piece and a solid electrolyte to prepare a solid-state electricity-buckling battery;
the specific electrochemical test mode of this example is the same as that of example 1, and the specific test data are shown in tables 1 and 2.
Table 1 examples 1 to 3 lithium ion batteries remaining percentage of capacity and remaining gram capacity mAh/g after 50 weeks cycling
| Item | Percentage of capacity remaining | Residual gram capacity |
| Example 1 | 97％ | 353 |
| Example 2 | 96％ | 347 |
| Example 3 | 96％ | 339 |
Table 2 examples 1 to 3 lithium ion batteries with different multiplying powers and gram capacities mAh/g
| Item | 0.5C | 1C | 2C | 5C | 10C | 20C |
| Example 1 | 369 | 357 | 341 | 331 | 322 | 306 |
| Example 2 | 364 | 354 | 335 | 327 | 315 | 302 |
| Example 3 | 356 | 345 | 325 | 318 | 306 | 295 |
Combining the data in tables 1 and 2, FeF3·0.33H2After the O-mesoporous carbon is mixed with sulfide, the gram capacity at 0.5 ℃ is more than 350mAh/g, and the voltage is at1.7-4.5V, the lithium ion batteries of examples 1-3 have the characteristics of high voltage and high capacity, and have excellent cycle performance and rate performance, and after 50 weeks of cycle, the capacity retention rate is more than 96%, which is far greater than the reported data.
The anode material provided by the invention has the advantages of high voltage and high gram capacity integrally, is suitable for being applied to a solid-state battery system, has higher gram capacity than the reported anode material, has the advantage of high voltage, meets the development requirement of the current lithium ion battery, and is an anode material combination with better prospect.
Claims (10)
1. The utility model provides a spacing compound ferric trifluoride cathode material which characterized in that: FeF synthesized from carbon material and iron salt by liquid phase synthesis method3·0.33H2An O-carbon material;
the carbon material is graphene or mesoporous carbon.
2. A method for preparing a limiting composite ferric trifluoride anode material according to claim 1, wherein:
the method comprises the following steps:
dispersing a carbon material in concentrated nitric acid, refluxing, and carrying out suction filtration on a refluxed solution to obtain a pure carbon material;
step two, ultrasonically dispersing the pure carbon material prepared in the step one in absolute ethyl alcohol;
step three, adding Fe (NO)3)3·9H2O and [ Bmim ]][BF4]Adding the ionic liquid into the absolute ethyl alcohol with the uniformly dispersed carbon material obtained in the third step;
and step four, stirring the mixture obtained in the step three at the first temperature for reacting for a period of time, heating to a second temperature, finishing the reaction at the second temperature, cleaning, and drying to obtain the powdery ferric fluoride-carbon material.
3. The method of claim 2, wherein: step four the product was rinsed with acetone.
4. The method of claim 2, wherein: fe (NO)3)3·9H2The amount of O is 2 to 5 times the amount of the carbon material, [ Bmim ]][BF4]The amount of the substance of the ionic liquid is 20 to 30 times the amount of the substance of the carbon material.
5. The method of claim 2, wherein: the amount of the anhydrous ethanol substance is 30 to 50 times the amount of the carbon material substance.
6. The method of claim 2, wherein:
in the fourth step
The first temperature is in the range of 0 to 5 ℃;
the second temperature is 60 to 80 ℃, and the reaction time at the second temperature is 6 to 10 hours.
7. A solid state lithium ion battery, characterized by: a positive electrode, a negative electrode and a solid electrolyte, the positive electrode comprising the FeF of claim 13·0.33H2An O-carbon material.
8. The lithium ion battery of claim 6, characterized in that:
the positive electrode also comprises sulfide, and the sulfide is one or more of iron sulfide, cobalt sulfide and tungsten sulfide.
9. The lithium ion battery of claim 7, characterized in that: FeF3·0.33H2The mass ratio of the O-carbon material to the sulfide is:
6: 4 to 8: 2.
10. the lithium ion battery of any of claims 6 to 8, wherein: the negative electrode is a lithium sheet.
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