CN115943121A - Energy composite material for lithium battery and preparation method thereof - Google Patents
Energy composite material for lithium battery and preparation method thereof Download PDFInfo
- Publication number
- CN115943121A CN115943121A CN201780098263.2A CN201780098263A CN115943121A CN 115943121 A CN115943121 A CN 115943121A CN 201780098263 A CN201780098263 A CN 201780098263A CN 115943121 A CN115943121 A CN 115943121A
- Authority
- CN
- China
- Prior art keywords
- composite material
- carbon matrix
- plant carbon
- energy composite
- lithium battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 77
- 229910052799 carbon Inorganic materials 0.000 claims description 73
- 239000011159 matrix material Substances 0.000 claims description 71
- 241000196324 Embryophyta Species 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 42
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000001816 cooling Methods 0.000 claims description 34
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 17
- 230000021523 carboxylation Effects 0.000 claims description 17
- 238000006473 carboxylation reaction Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 16
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 235000014676 Phragmites communis Nutrition 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 240000003826 Eichhornia crassipes Species 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 2
- 238000001994 activation Methods 0.000 description 15
- 230000004913 activation Effects 0.000 description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 8
- 230000002708 enhancing effect Effects 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 3
- 241000169203 Eichhornia Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000089486 Phragmites australis subsp australis Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000005068 transpiration Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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 discloses an energy composite material for a lithium battery and a preparation method thereof. The invention reduces the raw material acquisition cost of the energy composite material, reduces the requirement on process equipment, simplifies the process flow, reduces the pore diameter modification engineering of the raw material in the preparation of the energy composite material, reduces the manufacturing cost of the energy composite material, can efficiently convey the electrolyte based on the natural pore channel structure of the plant, is beneficial to improving the circulation efficiency of conductive ions and is beneficial to the efficient circulation of the conductive liquid.
Description
The invention relates to the technical field of functional composite materials, in particular to an energy composite material for a lithium battery and a preparation method thereof.
Since the business of the twenty-century and the ninety years, the lithium battery is widely applied to electronic devices, such as mobile phones, flat panels, cameras, new energy power automobiles and the like, by virtue of the characteristics of high energy density, high charge-discharge cycle efficiency and the like.
In the prior art, electrodes of lithium batteries are mainly made of graphite materials, the theoretical capacity of the electrode materials made of the graphite materials is limited, and the research and development of high-capacity negative electrode materials are always the main pointsThe general pursuit of those skilled in the art. Many practices prove that the material with higher theoretical capacity shows the problem of poor cycle performance in electrode reaction, such as the tin oxide material, the theoretical capacity reaches 790mA/g, and the self-discharge voltage<1.5V, but the tin oxide material is easy to agglomerate in the charging and discharging process, the structure of an electrode material is affected, the volume change of the battery is caused, the battery capacity is reduced, and the cycling stability is poor. Carbon materials have a low theoretical capacity but a high cycling stability, and functional engineering of carbon materials has been a general endeavor of those skilled in the art. For example, chinese patent publication No. CN103840137B discloses Fe prepared from water hyacinth 3 O 4 The preparation method disclosed in the specification of the patent improves the heavy metal pollution of the environment, has the characteristics of wide raw material source, easy industrial implementation, simple preparation process and environmental friendliness, and the prepared Fe 3 O 4 the/C composite material has good cycle performance and coulombic efficiency when being applied as a lithium ion battery cathode material. For example, "design Synthesis of CoaxialsSnO", published in Aavanced materials, 2009, no. 21, page 2536 2 carbon HollowNanospheres for high-grade Reversal lithium storage "(" design and assembly of carbon-coated tin dioxide hollow nanospheres for high-reversibility lithium batteries), can be used for preparing tin dioxide hollow nanospheres coated with carbon layers, and can relieve volume change of tin dioxide materials in the charging and discharging processes.
In the charge and discharge processes of a lithium battery, the specific surface area and the conductivity of an electrode material become critical factors affecting energy efficiency in the processes of lithium removal and lithium insertion. The conventional carbon material can ensure good conduction of lithium ions to a certain extent, and has better thermodynamic and chemical stability. However, the existing process for designing the functional structure of the carbon material has the problems of less raw materials, more preparation process steps, higher preparation cost and the like. In summary, in the prior art, few energy functional composite materials are prepared by directly utilizing the self structure of plants, and resources given to nature by human beings are not fully utilized.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an energy composite material for a lithium battery and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: a preparation method of an energy composite material for a lithium battery comprises the following steps:
(1) Selecting stems or leaves of plants with porous structures as raw materials, drying, and carbonizing the dried stems or leaves at 660-720 ℃;
(2) Mixing the stem or leaf powder after carbonization with sodium hydroxide powder according to the mass ratio of 1:3 to obtain mixed powder, calcining the mixed powder for 1-2 hours at 810-1000 ℃ in nitrogen atmosphere, and cooling to room temperature;
(3) Mixing the mixture obtained after the calcination in the step (2) with iron oxide according to a mass ratio of 1:1, calcining for 2-4 hours at 600-700 ℃ in a nitrogen atmosphere, cooling, adding 10-12 wt% of dilute hydrochloric acid solution, washing away iron oxide impurities to obtain a mixed solution with a mass concentration of 8-11 g/L, stirring the mixed solution at 60-80 ℃ while heating in a water bath for 3-4 hours, washing with water until the solution is neutral, filtering, and drying to obtain the plant carbon matrix material;
(4) Mixing the plant carbon matrix material obtained in the step (3) with a strong acid solution with the mass concentration of 65-75% for carboxylation treatment to obtain a plant carbon matrix mixed solution with the mass concentration of 0.6000 g/L-0.8000 g/L, reacting the plant carbon matrix mixed solution at 85-90 ℃ for 180-270 min, filtering, washing with water until the solution is neutral, and drying in vacuum to obtain a plant carbon matrix powder material after carboxylation treatment;
(5) Mixing the plant carbon matrix powder material obtained in the step (4) with stannous oxide according to the mass ratio of 1:3, adding ethanol and distilled water for stirring, performing ultrasonic treatment for 4.5-6.5 h, performing suction filtration, and performing vacuum drying to obtain a composite material;
(6) And (3) putting the composite material obtained in the step (5) into a tubular furnace, vacuumizing the tubular furnace, starting a temperature control power supply when the pressure in the tubular furnace is less than 0.08MPa, heating to 400-500 ℃ at the heating rate of 5-8 ℃/min, introducing nitrogen, preserving the heat for 3.5-4.5 h, finally cooling to 300 ℃ at the rate of 1-2 ℃/min, closing the power supply, and naturally cooling to room temperature to obtain the energy composite material.
Further, in the step (1), the plant is at least one of reed and water hyacinth.
Further, in the step (4), the vacuum drying temperature is 50-60 ℃, and the drying time is 12-36 h.
Further, in the step (6), the temperature is raised to 450-460 ℃ at a heating rate of 6.5-6.8 ℃/min.
Further, in the step (6), the cooling rate is 1 ℃/min to 1.5 ℃/min.
And the energy composite material for the lithium battery prepared by the preparation method in any one of the above technical schemes.
The invention has the beneficial effects that:
(1) The invention firstly adopts reed plants and the like to carry out carbonization treatment, extracts carbon matrix materials, and mixes and calcines the extracted carbon matrix materials through sodium hydroxide for activation treatment, then mixes the activated carbon matrix materials with ferric oxide for calcination treatment at high temperature, the ferric oxide is used as a catalyst to induce the carbon matrix materials to be converted into graphite and graphene-like net structure materials at high temperature, the transport capacity of the graphite and graphene-like net structure to electrons is stronger than that of amorphous carbon, the electric conductivity of the carbon matrix materials is improved after the high-temperature calcination and the catalyst coaction, the carbon matrix materials can transport moisture absorbed by roots to leaves due to the plant transpiration, the stems and the leaves play the roles of transporting substances and exchanging energy in the growth and metabolism of the whole plant, the living body structure is beneficial to the high-efficiency circulation of liquid, and the plant materials after carbonization, activation and high-temperature calcination catalysis can efficiently transport conductive ions in electrolyte, thereby being beneficial to the improvement of the circulation efficiency of the conductive ions.
(2) The invention directly utilizes the liquid conveying channel formed by plants based on matter exchange and energy flow to transmit conductive ions, thereby reducing complex aperture modification engineering and reducing the processing and manufacturing cost of aperture materials in energy composite materials.
(3) According to the invention, the plant carbon matrix material is subjected to carboxylation treatment in a strong acid solution, the activity of the reaction sites of the plant carbon matrix material is improved by utilizing the strong oxidizing property of the strong acid, the activation energy of the reaction sites is enhanced, when the stannous oxide and the plant carbon matrix material are compounded, the stannous oxide material can be promoted to be uniformly distributed on the plant carbon matrix material, the compounding of the plant carbon matrix material and the stannous oxide is promoted, and the strong acid solution can be a nitric acid solution, a concentrated sulfuric acid solution and the like.
The technical effects of the present invention are not limited to the above, the above technical effects are merely exemplary illustrations, and other features of the present invention and its actions and the like will be described in detail in the following detailed description. Those skilled in the art can directly or indirectly know the remaining technical effects and the like according to the description of the present application, and the detailed description is omitted.
Reference will now be made in detail to the present embodiments of the invention, all features disclosed in this specification, or all methods or process steps disclosed as implicit, may be combined in any manner, except for the mutually exclusive features and/or steps. The embodiments described herein are merely illustrative and are not intended to limit the present invention. In the following description, it will be apparent to those of ordinary skill in the art that: it is not necessary to employ these specific details to practice the present invention. In other instances, well known processes, well known auxiliary additives or well known implementation equipment, and the like, have not been described in detail in order to avoid obscuring the present invention.
[ EXAMPLES one ]
A preparation method of an energy composite material for a lithium battery comprises the following steps:
(1) Selecting stems or leaves of reed as raw materials, drying, and carbonizing the dried stems or leaves at 700 ℃ to extract a carbon matrix material;
(2) Mixing the stem or leaf powder subjected to carbonization treatment with sodium hydroxide powder according to a mass ratio of 1:3 to obtain mixed powder, calcining the mixed powder at 900 ℃ for 1.5h in a nitrogen atmosphere, performing activation treatment, and cooling to room temperature;
(3) Mixing the mixture obtained after calcination in the step (2) with iron oxide according to a mass ratio of 1:1, calcining for 3 hours at 650 ℃ in a nitrogen atmosphere, cooling, adding 11wt% of dilute hydrochloric acid solution for washing away iron oxide impurities to obtain a mixed solution with a mass concentration of 9g/L, heating the mixed solution in a water bath for 3.5 hours at 70 ℃ while stirring, washing with water until the solution is neutral, filtering, and drying to obtain a plant carbon matrix material;
(4) Mixing the plant carbon matrix material obtained in the step (3) with a strong acid solution with the mass concentration of 70% for carboxylation treatment, wherein the strong acid solution is used for enhancing the activation energy of the plant carbon matrix material to obtain a plant carbon matrix mixed solution with the mass concentration of 0.7000g/L, reacting the plant carbon matrix mixed solution at 87 ℃ for 220min, filtering, washing with water until the solution is neutral, and drying in vacuum to obtain a plant carbon matrix powder material after carboxylation treatment;
(5) Mixing the plant carbon matrix powder material in the step (4) with stannous oxide according to a mass ratio of 1:3, adding ethanol and distilled water for stirring, performing ultrasonic treatment for 5 hours, performing suction filtration, and performing vacuum drying to obtain a composite material, wherein the circulation stability of the stannous oxide can be improved;
(6) And (3) putting the composite material obtained in the step (5) into a tubular furnace, vacuumizing the tubular furnace, starting a temperature control power supply when the pressure in the tubular furnace is less than 0.08MPa, heating to 450 ℃ at the heating rate of 6 ℃/min, introducing nitrogen, preserving heat for 4 hours, finally cooling to 300 ℃ at the speed of 1.5 ℃/min, closing the power supply, and naturally cooling to room temperature to obtain the energy composite material.
[ example two ]
A preparation method of an energy composite material for a lithium battery comprises the following steps:
(1) Selecting stems or leaves of reed as raw materials, drying, and carbonizing the dried stems or leaves at 720 ℃ to extract a carbon matrix material;
(2) Taking the stem or leaf powder after carbonization, adding sodium hydroxide powder, mixing according to the mass ratio of 1:3 to obtain mixed powder, calcining the mixed powder for 1.5 hours at 1000 ℃ in a nitrogen atmosphere, performing activation treatment, and cooling to room temperature;
(3) Mixing the mixture obtained after calcination in the step (2) with iron oxide according to a mass ratio of 1:1, calcining for 3 hours at 700 ℃ in a nitrogen atmosphere, cooling, adding 11wt% of dilute hydrochloric acid solution for washing away iron oxide impurities to obtain a mixed solution with a mass concentration of 9g/L, heating the mixed solution in a water bath for 3.5 hours at 80 ℃ while stirring, washing with water until the solution is neutral, filtering, and drying to obtain a plant carbon matrix material;
(4) Mixing the plant carbon matrix material obtained in the step (3) with a strong acid solution with the mass concentration of 70% for carboxylation treatment, wherein the strong acid solution is used for enhancing the activation energy of the plant carbon matrix material to obtain a plant carbon matrix mixed solution with the mass concentration of 0.7000g/L, reacting the plant carbon matrix mixed solution at 90 ℃ for 220min, filtering, washing with water until the solution is neutral, and drying in vacuum to obtain a plant carbon matrix powder material after carboxylation treatment;
(5) Mixing the plant carbon matrix powder material in the step (4) with stannous oxide according to a mass ratio of 1:3, adding ethanol and distilled water for stirring, performing ultrasonic treatment for 5 hours, performing suction filtration, and performing vacuum drying to obtain a composite material, wherein the circulation stability of the stannous oxide can be improved;
(6) And (3) putting the composite material obtained in the step (5) into a tubular furnace, vacuumizing the tubular furnace, starting a temperature control power supply when the pressure in the tubular furnace is less than 0.08MPa, heating to 450 ℃ at the heating rate of 6 ℃/min, introducing nitrogen, preserving heat for 4 hours, finally cooling to 300 ℃ at the speed of 1.5 ℃/min, closing the power supply, and naturally cooling to room temperature to obtain the energy composite material.
[ EXAMPLE III ]
A preparation method of an energy composite material for a lithium battery comprises the following steps:
(1) Selecting stems or leaves of reed as raw materials, drying, and carbonizing the dried stems or leaves at 660 ℃ to extract a carbon matrix material;
(2) Mixing the stem or leaf powder subjected to carbonization treatment with sodium hydroxide powder according to a mass ratio of 1:3 to obtain mixed powder, calcining the mixed powder for 1.5 hours at 810 ℃ in a nitrogen atmosphere, performing activation treatment, and cooling to room temperature;
(3) Mixing the mixture obtained after calcination in the step (2) with iron oxide according to a mass ratio of 1:1, calcining for 3 hours at 600 ℃ in a nitrogen atmosphere, cooling, adding 11wt% of dilute hydrochloric acid solution for washing away iron oxide impurities to obtain a mixed solution with a mass concentration of 9g/L, heating the mixed solution in a water bath for 3.5 hours at 60 ℃ while stirring, washing with water until the solution is neutral, filtering, and drying to obtain a plant carbon matrix material;
(4) Mixing the plant carbon matrix material obtained in the step (3) with a strong acid solution with the mass concentration of 70% for carboxylation treatment, wherein the strong acid solution is used for enhancing the activation energy of the plant carbon matrix material to obtain a plant carbon matrix mixed solution with the mass concentration of 0.7000g/L, reacting the plant carbon matrix mixed solution at 85 ℃ for 220min, filtering, washing with water until the solution is neutral, and drying in vacuum to obtain a plant carbon matrix powder material after carboxylation treatment;
(5) Mixing the plant carbon matrix powder material in the step (4) with stannous oxide according to a mass ratio of 1:3, adding ethanol and distilled water for stirring, performing ultrasonic treatment for 5 hours, performing suction filtration, and performing vacuum drying to obtain a composite material, wherein the circulation stability of the stannous oxide can be improved;
(6) And (4) putting the composite material obtained in the step (5) into a tubular furnace, vacuumizing the tubular furnace, starting a temperature control power supply when the pressure in the tubular furnace is less than 0.08MPa, heating to 450 ℃ at the heating rate of 6 ℃/min, introducing nitrogen, keeping the temperature for 4 hours, cooling to 300 ℃ at the temperature of 1.5 ℃/min, closing the power supply, and naturally cooling to room temperature to obtain the energy composite material.
[ EXAMPLE IV ]
A preparation method of an energy composite material for a lithium battery comprises the following steps:
(1) Selecting stems or leaves of reed as raw materials, drying, and carbonizing the dried stems or leaves at 720 ℃ to extract a carbon matrix material;
(2) Mixing the stem or leaf powder subjected to carbonization treatment with sodium hydroxide powder according to a mass ratio of 1:3 to obtain mixed powder, calcining the mixed powder for 2 hours at 1000 ℃ in a nitrogen atmosphere, performing activation treatment, and cooling to room temperature;
(3) Mixing the mixture obtained after calcination in the step (2) with iron oxide according to a mass ratio of 1:1, calcining for 4 hours at 700 ℃ in a nitrogen atmosphere, cooling, adding 11wt% of dilute hydrochloric acid solution for washing away iron oxide impurities to obtain a mixed solution with a mass concentration of 9g/L, heating the mixed solution in a water bath for 4 hours at 80 ℃ while stirring, washing with water until the solution is neutral, filtering, and drying to obtain a plant carbon matrix material;
(4) Mixing the plant carbon matrix material obtained in the step (3) with a strong acid solution with the mass concentration of 70% for carboxylation treatment, wherein the strong acid solution is used for enhancing the activation energy of the plant carbon matrix material to obtain a plant carbon matrix mixed solution with the mass concentration of 0.7000g/L, reacting the plant carbon matrix mixed solution at 90 ℃ for 270min, filtering, washing with water until the solution is neutral, and drying in vacuum to obtain a plant carbon matrix powder material after carboxylation treatment;
(5) Mixing the plant carbon matrix powder material in the step (4) with stannous oxide according to a mass ratio of 1:3, adding ethanol and distilled water for stirring, performing ultrasonic treatment for 6.5 hours, performing suction filtration, and performing vacuum drying to obtain a composite material, wherein the circulation stability of the stannous oxide can be improved;
(6) And (3) putting the composite material obtained in the step (5) into a tubular furnace, vacuumizing the tubular furnace, starting a temperature control power supply when the pressure in the tubular furnace is less than 0.08MPa, heating to 450 ℃ at the heating rate of 6 ℃/min, introducing nitrogen, preserving heat for 4.5 hours, finally cooling to 300 ℃ at the speed of 1.5 ℃/min, closing the power supply, and naturally cooling to room temperature to obtain the energy composite material.
[ EXAMPLE V ]
A preparation method of an energy composite material for a lithium battery comprises the following steps:
(1) Selecting stems or leaves of reeds as raw materials, drying, and carbonizing the dried stems or leaves at 660 ℃ to extract carbon matrix materials;
(2) Mixing the stem or leaf powder subjected to carbonization treatment with sodium hydroxide powder according to a mass ratio of 1:3 to obtain mixed powder, calcining the mixed powder for 1h at 810 ℃ in a nitrogen atmosphere, performing activation treatment, and cooling to room temperature;
(3) Mixing the mixture obtained after calcination in the step (2) with iron oxide according to a mass ratio of 1:1, calcining for 2 hours at 600 ℃ in a nitrogen atmosphere, cooling, adding 11wt% of dilute hydrochloric acid solution for washing away iron oxide impurities to obtain a mixed solution with a mass concentration of 9g/L, heating the mixed solution in a water bath for 3 hours at 60 ℃, washing with water until the solution is neutral, filtering, and drying to obtain a plant carbon matrix material;
(4) Mixing the plant carbon matrix material obtained in the step (3) with a strong acid solution with the mass concentration of 70% for carboxylation treatment, wherein the strong acid solution is used for enhancing the activation energy of the plant carbon matrix material to obtain a plant carbon matrix mixed solution with the mass concentration of 0.7000g/L, reacting the plant carbon matrix mixed solution at 85 ℃ for 180min, filtering, washing with water until the solution is neutral, and drying in vacuum to obtain a plant carbon matrix powder material after carboxylation treatment;
(5) Mixing the plant carbon matrix powder material in the step (4) with stannous oxide according to a mass ratio of 1:3, adding ethanol and distilled water for stirring, performing ultrasonic treatment for 4.5 hours, performing suction filtration, and performing vacuum drying to obtain a composite material, wherein the circulation stability of the stannous oxide can be improved;
(6) And (3) putting the composite material obtained in the step (5) into a tubular furnace, vacuumizing the tubular furnace, starting a temperature control power supply when the pressure in the tubular furnace is less than 0.08MPa, heating to 450 ℃ at the heating rate of 6 ℃/min, introducing nitrogen, preserving heat for 3.5 hours, finally cooling to 300 ℃ at the speed of 1.5 ℃/min, closing the power supply, and naturally cooling to room temperature to obtain the energy composite material.
[ EXAMPLE six ]
A preparation method of an energy composite material for a lithium battery comprises the following steps:
(1) Selecting stem or leaf of Eichhornia crassipes (Fr.) Crasslpes as raw material, drying, then carbonizing the dried stem or leaf at 700 ℃ to extract a carbon matrix material;
(2) Mixing the stem or leaf powder subjected to carbonization treatment with sodium hydroxide powder according to a mass ratio of 1:3 to obtain mixed powder, calcining the mixed powder at 900 ℃ for 1.5h in a nitrogen atmosphere, performing activation treatment, and cooling to room temperature;
(3) Mixing the mixture obtained after calcination in the step (2) with iron oxide according to a mass ratio of 1:1, calcining for 3 hours at 650 ℃ in a nitrogen atmosphere, cooling, adding 11wt% of dilute hydrochloric acid solution for washing away iron oxide impurities to obtain a mixed solution with a mass concentration of 9g/L, heating the mixed solution in a water bath for 3.5 hours at 70 ℃ while stirring, washing with water until the solution is neutral, filtering, and drying to obtain a plant carbon matrix material;
(4) Mixing the plant carbon matrix material obtained in the step (3) with a strong acid solution with the mass concentration of 70% for carboxylation treatment, wherein the strong acid solution is used for enhancing the activation energy of the plant carbon matrix material to obtain a plant carbon matrix mixed solution with the mass concentration of 0.7000g/L, reacting the plant carbon matrix mixed solution at 87 ℃ for 220min, filtering, washing with water until the solution is neutral, and drying in vacuum to obtain a plant carbon matrix powder material after carboxylation treatment;
(5) Mixing the plant carbon matrix powder material in the step (4) with stannous oxide according to a mass ratio of 1:3, adding ethanol and distilled water for stirring, performing ultrasonic treatment for 5 hours, performing suction filtration, and performing vacuum drying to obtain a composite material, wherein the circulation stability of the stannous oxide can be improved;
(6) And (3) putting the composite material obtained in the step (5) into a tubular furnace, vacuumizing the tubular furnace, starting a temperature control power supply when the pressure in the tubular furnace is less than 0.08MPa, heating to 450 ℃ at the heating rate of 6 ℃/min, introducing nitrogen, preserving heat for 4 hours, finally cooling to 300 ℃ at the speed of 1.5 ℃/min, closing the power supply, and naturally cooling to room temperature to obtain the energy composite material.
In the other technical features in the above embodiments, those skilled in the art can flexibly select and use the features according to actual situations to meet different specific actual requirements. However, it will be apparent to one of ordinary skill in the art that: it is not necessary to employ these specific details to practice the present invention. In other instances, well-known auxiliary materials, well-known process operation equipment, well-known material structures, well-known data, diagrams and the like are not specifically described in order to avoid obscuring the present invention and are within the technical scope defined by the technical scheme of the claims of the present invention.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
- A preparation method of an energy composite material for a lithium battery is characterized by comprising the following steps:(1) Selecting stems or leaves of plants with porous structures as raw materials, drying, and carbonizing the dried stems or leaves at 660-720 ℃;(2) Mixing the stem or leaf powder after carbonization with sodium hydroxide powder according to a mass ratio of 1:3 to obtain mixed powder, calcining the mixed powder at 810-1000 ℃ for 1-2 h in a nitrogen atmosphere, and cooling to room temperature;(3) Mixing the mixture obtained after the calcination in the step (2) with iron oxide according to a mass ratio of 1:1, calcining for 2-4 hours at 600-700 ℃ in a nitrogen atmosphere, cooling, adding 10-12 wt% of dilute hydrochloric acid solution, washing away iron oxide impurities to obtain a mixed solution with a mass concentration of 8-11 g/L, stirring the mixed solution at 60-80 ℃ while heating in a water bath for 3-4 hours, washing with water until the solution is neutral, filtering, and drying to obtain the plant carbon matrix material;(4) Mixing the plant carbon matrix material obtained in the step (3) with a strong acid solution with the mass concentration of 65-75% to perform carboxylation treatment to obtain a plant carbon matrix mixed solution with the mass concentration of 0.6000 g/L-0.8000 g/L, reacting the plant carbon matrix mixed solution at 85-90 ℃ for 180-270 min, filtering, washing with water until the solution is neutral, and performing vacuum drying to obtain a plant carbon matrix powder material after carboxylation treatment;(5) Mixing the plant carbon matrix powder material in the step (4) with stannous oxide according to the mass ratio of 1:3, adding ethanol and distilled water for stirring, performing ultrasonic treatment for 4.5-6.5 hours, performing suction filtration, and performing vacuum drying to obtain a composite material;(6) And (4) putting the composite material obtained in the step (5) into a tubular furnace, vacuumizing the tubular furnace, starting a temperature control power supply when the pressure in the tubular furnace is less than 0.08MPa, heating to 400-500 ℃ at the heating rate of 5-8 ℃/min, introducing nitrogen, keeping the temperature for 3.5-4.5 h, finally cooling to 300 ℃ at the temperature of 1-2 ℃/min, closing the power supply, and naturally cooling to room temperature to obtain the energy composite material.
- The method of claim 1, wherein in the step (1), the plant is at least one of reed and water hyacinth.
- The method for preparing an energy composite material for a lithium battery as claimed in claim 1, wherein the vacuum drying temperature is 50 ℃ to 60 ℃ and the drying time is 12 to 36 hours in step (4).
- The method for preparing an energy composite material for a lithium battery as claimed in claim 1, wherein the temperature is raised to 450-460 ℃ at a temperature raising rate of 6.5-6.8 ℃/min in the step (6).
- The method for preparing an energy composite material for a lithium battery as claimed in claim 1, wherein the cooling rate in the step (6) is 1 ℃/min to 1.5 ℃/min.
- An energy composite material for a lithium battery prepared by the preparation method as set forth in any one of claims 1 to 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2017/118676 WO2019127031A1 (en) | 2017-12-26 | 2017-12-26 | Energy composite material for lithium battery and preparation method therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115943121A true CN115943121A (en) | 2023-04-07 |
Family
ID=67064256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780098263.2A Pending CN115943121A (en) | 2017-12-26 | 2017-12-26 | Energy composite material for lithium battery and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115943121A (en) |
| WO (1) | WO2019127031A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111847525B (en) * | 2020-07-29 | 2023-06-13 | 安徽工程大学 | Green synthetic magnetic nano Fe for water hyacinth 3 O 4 Method and use of particles |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN101872651A (en) * | 2010-06-22 | 2010-10-27 | 上海交通大学 | Method for preparing in-situ self-grown nano carbon composite material |
| CN103579640A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Anode material for lithium-air battery and preparation method thereof |
| CN107265436A (en) * | 2017-07-31 | 2017-10-20 | 武汉大学 | The preparation method and applications of biomass graphitized stephanoporate material with carbon element |
| CN107359329A (en) * | 2017-07-03 | 2017-11-17 | 东北师范大学 | Carbon coating stannous oxide compound and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9147874B2 (en) * | 2012-06-11 | 2015-09-29 | Nanotek Instruments, Inc. | Rechargeable lithium cell having a meso-porous conductive material structure-supported phthalocyanine compound cathode |
| CN104016341B (en) * | 2014-07-01 | 2016-11-16 | 济南圣泉集团股份有限公司 | A kind of preparation method of porous graphene |
-
2017
- 2017-12-26 CN CN201780098263.2A patent/CN115943121A/en active Pending
- 2017-12-26 WO PCT/CN2017/118676 patent/WO2019127031A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN101872651A (en) * | 2010-06-22 | 2010-10-27 | 上海交通大学 | Method for preparing in-situ self-grown nano carbon composite material |
| CN103579640A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Anode material for lithium-air battery and preparation method thereof |
| CN107359329A (en) * | 2017-07-03 | 2017-11-17 | 东北师范大学 | Carbon coating stannous oxide compound and its preparation method and application |
| CN107265436A (en) * | 2017-07-31 | 2017-10-20 | 武汉大学 | The preparation method and applications of biomass graphitized stephanoporate material with carbon element |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019127031A1 (en) | 2019-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111362254B (en) | Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material | |
| CN109449417B (en) | Sodium iron phosphate composite cathode material and preparation method and application thereof | |
| CN105439128A (en) | Preparation method for porous graphene lithium ion battery positive electrode material | |
| CN109755540B (en) | Lithium-sulfur battery positive electrode material and preparation method thereof | |
| CN109686948B (en) | Preparation method of composite positive electrode material of lithium-sulfur battery | |
| CN103730638A (en) | Preparation method of nitrogen-doped carbon material | |
| CN113054183A (en) | Preparation method of CoNi bimetal organic framework derived carbon-sulfur composite material | |
| CN103346297A (en) | Preparation method for carbon coated composite metal oxide electrode material | |
| CN111276679A (en) | Double-carbon composite molybdenum sulfide composite material for sodium ion battery cathode material and preparation method thereof | |
| CN113948681B (en) | Biomass-based hard carbon compound composite material and preparation method and application thereof | |
| CN109817923A (en) | A kind of nitrogen-doped porous carbon material and its preparation method and application | |
| CN106299282A (en) | A kind of nitrogen-doped carbon nanometer pipe sulfur composite and preparation method | |
| CN115020681A (en) | Carbon-coated sodium ferric sulfate cathode material and preparation method thereof | |
| CN112599770A (en) | Lithium/sodium ion battery negative electrode material and preparation method thereof | |
| CN114477300B (en) | Sodium ion battery positive electrode material and preparation method and application thereof | |
| CN107946548B (en) | Preparation method of lithium-iron oxide and carbon composite lithium ion battery anode material | |
| CN107978745B (en) | High-capacity carbon nanotube composite cobalt sulfide negative electrode material and preparation and application thereof | |
| CN109301223A (en) | Anode composite material of lithium sulfur battery and preparation method thereof | |
| CN113421990A (en) | Iron-based biomass carbon intermediate layer of lithium-sulfur battery, preparation method and lithium-sulfur battery | |
| CN113161533A (en) | MOF-derived ZnO @ C composite material and application thereof | |
| CN112299389A (en) | Method for preparing sodium ion carbon negative electrode material by using nitrogen-doped porous biomass carbon | |
| CN115943121A (en) | Energy composite material for lithium battery and preparation method thereof | |
| CN108155378A (en) | A kind of preparation based on graphene high energy lithium ion cell negative material | |
| CN105449176B (en) | A kind of long-life lead carbon battery pole plate of modified activated carbon | |
| CN111517297B (en) | Preparation method and application of heterostructure/graphene composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |