CN114242947A - Carbon-coated lithium phosphide electrode and preparation method thereof - Google Patents
Carbon-coated lithium phosphide electrode and preparation method thereof Download PDFInfo
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- CN114242947A CN114242947A CN202111580439.2A CN202111580439A CN114242947A CN 114242947 A CN114242947 A CN 114242947A CN 202111580439 A CN202111580439 A CN 202111580439A CN 114242947 A CN114242947 A CN 114242947A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 66
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000002023 wood Substances 0.000 claims abstract description 116
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 19
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 15
- 239000008103 glucose Substances 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 14
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 6
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 62
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 48
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000002791 soaking Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 229920002522 Wood fibre Polymers 0.000 claims description 2
- 239000002025 wood fiber Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 238000003763 carbonization Methods 0.000 abstract description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/5805—Phosphides
-
- 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 a carbon-coated lithium phosphide electrode and a preparation method thereof; the electrode includes a carbon substrate; micron-sized pore channels are arranged on the carbon substrate; lithium phosphide is filled in the micron-sized pore channel; the carbon matrix is obtained by carbonizing wood chips; the micron-sized pore channels are pore channels in the wood chips. According to the invention, lithium phosphate adsorbed in wood chips is converted into lithium phosphide by calcination only in the last step, glucose and the wood chips are converted into carbon, so that the lithium phosphide electrode is directly obtained, and lithium phosphide materials do not participate in the previous steps, so that the steps needing a drying environment in the lithium phosphide preparation process are greatly reduced, the process is obviously simplified, and the cost brought by providing the drying environment for the lithium phosphide is saved. In addition, the lithium phosphide is coated by glucose and carbon obtained after wood chip carbonization, so that the electronic conductivity of the lithium phosphide electrode can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a carbon-coated lithium phosphide electrode and a preparation method thereof.
Background
With the gradual depletion of fossil energy and the environmental pollution problem caused by the use of fossil energy, the utilization of renewable energy is imminent. However, renewable energy sources are characterized by instability. To be better able to store it, we often need to store it. The charge-discharge battery has the function of converting electric energy into chemical energy for storage and then converting the chemical energy into electric energy for use, thereby playing an important role in the field of new energy utilization. Since the performance of the lithium ion battery approaches the theoretical limit, in order to improve the specific energy of the lithium ion battery, it is necessary to develop an electrode material with higher specific capacity. Lithium phosphide is of particular interest because of its extremely high specific capacity (1550 mAh/g). However, commercialization of lithium phosphide electrodes still faces some problems.
In the prior art, lithium phosphide is mainly obtained by directly reacting elemental phosphorus with elemental lithium, so that the lithium phosphide participates in the whole process of preparing a lithium phosphide electrode (comprising slurry preparation, pole piece coating, pole piece rolling and the like); lithium phosphide is extremely unstable in air and is easy to react with water to generate lithium hydroxide and extremely toxic phosphine, so that the whole production process of the lithium phosphide electrode needs to be carried out in an extremely dry environment, and the production cost is greatly increased. In addition, lithium phosphide has a characteristic of poor electron conductivity. Researchers typically subject lithium phosphide to mechanical ball milling with carbon materials to improve the electronic conductivity of the electrode. However, since lithium phosphide has a high mechanical strength, mechanical ball milling cannot effectively mix it with a carbon material. Therefore, there is still a need for a more efficient method for preparing a lithium phosphide electrode material, which on the one hand reduces the flow in a dry atmosphere during the production of the lithium phosphide electrode, and on the other hand enhances the bonding with carbon materials.
Disclosure of Invention
The invention aims to solve the technical problems and provides a carbon-coated lithium phosphide electrode and a preparation method and application thereof.
In a first aspect, the present invention provides a carbon-coated lithium phosphide electrode comprising a carbon matrix; micron-sized pore channels are arranged on the carbon substrate; lithium phosphide is filled in the micron-sized pore channel; the carbon matrix is obtained by carbonizing wood chips; the micron-sized pore channels are pore channels in the wood chips.
In a second aspect, the present invention provides a method for preparing a carbon-coated lithium phosphide electrode, which comprises the following specific steps:
step one, obtaining wood chips with fiber directions parallel to the thickness direction.
And step two, heating the wood chips in an alkali solution and an acid solution in sequence.
And step three, drying the wood chips, and then sequentially soaking the wood chips in a phosphoric acid solution and a lithium chloride solution to enable the phosphoric acid solution and the lithium chloride solution to enter pores in the wood chips along the fiber direction. The soaking of the wood chips in the phosphoric acid solution and the lithium chloride solution is performed once or repeatedly.
And step four, heating the wood chips treated in the step three in a glucose solution and then drying.
And step five, heating the wood chips treated in the step four in a dry environment to carbonize the wood chips and glucose, and reacting lithium phosphate with carbon to form lithium phosphide, so as to obtain the carbon-coated lithium phosphide electrode.
Preferably, the thickness of the wood chips in the first step is 500-800 μm.
Preferably, the wood chips in the first step are cut by a knife along the direction perpendicular to the wood fiber and then ground.
Preferably, in the second step, the wood chips are heated in the alkali solution and the acid solution and then washed to be neutral by deionized water respectively. The alkali solution is 1M sodium hydroxide solution; the acid solution was 1M hydrochloric acid solution.
Preferably, the heating temperature of the second step in the alkali solution and the acid solution is 80 ℃, and the heating time is 2 h.
Preferably, in the third step, the molar concentration of the phosphoric acid solution is 0.1-0.5M; the molar concentration of the lithium chloride solution was 3 times that of the phosphoric acid solution.
Preferably, in the third step, the wood chips are soaked in the phosphoric acid solution and the lithium chloride solution for 10min at the temperature of 80 ℃; and taking out the phosphoric acid solution and the lithium chloride solution from the wood chip, and then respectively swinging and washing in deionized water for 5 s.
Preferably, in the third step, the soaking of the wood chips in the phosphoric acid solution and the lithium chloride solution is repeatedly performed for 1 to 60 times.
Preferably, in the fourth step, the glucose solution has a mass fraction of 50%, a heating temperature of 80 ℃ and a heating time of 1 h.
Preferably, in the fifth step, the wood chips are heated to 700-900 ℃ at the speed of 2 ℃/min in the argon atmosphere, and are naturally cooled after being kept for 2 h.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, lithium phosphate adsorbed in wood chips is converted into lithium phosphide by calcination only in the last step, glucose and the wood chips are converted into carbon, so that the lithium phosphide electrode is directly obtained, and lithium phosphide materials do not participate in the previous steps, so that the steps needing a drying environment in the lithium phosphide preparation process are greatly reduced, the process is obviously simplified, and the cost brought by providing the drying environment for the lithium phosphide is saved. In addition, the lithium phosphide is coated by glucose and carbon obtained after wood chip carbonization, so that the electronic conductivity of the lithium phosphide electrode can be effectively improved. The wood chips have micron channels in the fiber direction, and conditions are provided for adsorbing phosphoric acid and lithium chloride and reacting the phosphoric acid and the lithium chloride. Also, the microchannels remain after carbonization. Lithium phosphate crystallization and lithium phosphide formation are confined to the microchannel, which effectively suppresses the size of the resulting lithium phosphide. The carbon-coated lithium phosphide is positioned in the micron channel in the carbonized wood chip, namely a transmission channel of ions during charging and discharging of the battery. This configuration facilitates the transport of ions. The improvement of the electronic and ionic conductivity can effectively improve the electrochemical performance of the lithium phosphide electrode. Therefore, the invention has the following advantages:
(1) the invention greatly saves the cost brought by providing a drying environment for the lithium phosphide.
(2) The lithium phosphide particles are coated by carbon, so that the electronic conductivity of the lithium phosphide electrode can be effectively improved.
(3) The invention utilizes wood derived carbon materials to promote lithium ion transport by virtue of micron channels carried by the wood derived carbon materials in the fiber direction.
(4) Lithium phosphate crystallization and lithium phosphide generation are limited in the micro-channel, so that the size of the obtained lithium phosphide can be effectively inhibited, and the electronic conductivity and the ionic conductivity of the lithium phosphide electrode are improved.
Drawings
Fig. 1 is a cycle capacity curve of a lithium phosphide electrode of example 1 of the present invention at a charge-discharge current of 0.2C.
Detailed Description
In order to better explain the process and scheme of the present invention, the following invention is further described with reference to the accompanying drawings and examples. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Example 1
As shown in fig. 1, a method for preparing a carbon-coated lithium phosphide electrode comprises the following steps:
s1, cutting off 1500 μm thick wood chips along the direction perpendicular to the fiber direction by a knife and sanding to 500 μm.
S2, the polished wood chips are heated for 2 hours at 80 ℃ by using 1M sodium hydroxide solution and then are washed to be neutral by using deionized water.
S3, heating the wood chips treated in the step S2 at 80 ℃ for 2h by using 1M hydrochloric acid solution, washing the wood chips to be neutral by using deionized water, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
S4, preparing 0.1M phosphoric acid solution and preparing 3 times of lithium chloride solution with the concentration of the phosphoric acid solution.
S5, soaking the wood chips obtained in the step S3 in a phosphoric acid solution at 80 ℃ for 10min, then swinging and washing the wood chips in deionized water for 5S, then soaking the wood chips in a lithium chloride solution at 80 ℃ for 10min, then swinging and washing the wood chips in deionized water for 5S, and repeating the step for 60 times.
S6, putting the wood chips treated in the step S5 into a glucose solution with the mass fraction of 50%, heating the wood chips at 80 ℃ for 1h, taking the wood chips out, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
And S7, heating the wood chips treated in the step S6 to 800 ℃ at a speed of 2 ℃/min in an argon atmosphere, keeping for 2 hours, and naturally cooling to obtain the carbon-coated lithium phosphide electrode.
Example 2
A preparation method of a carbon-coated lithium phosphide electrode comprises the following specific steps:
s1, cutting off 1500 μm thick wood chips along the direction perpendicular to the fiber direction by a knife and sanding to 800 μm.
S2, the polished wood chips are heated for 2 hours at 80 ℃ by using 1M sodium hydroxide solution and then are washed to be neutral by using deionized water.
S3, heating the wood chips treated in the step S2 at 80 ℃ for 2h by using 1M hydrochloric acid solution, washing the wood chips to be neutral by using deionized water, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
S4, preparing 0.5M phosphoric acid solution and preparing 3 times of lithium chloride solution with the concentration of the phosphoric acid solution.
And S5, soaking the wood chips obtained in the step S3 in a phosphoric acid solution at 80 ℃ for 10min, then swinging and washing the wood chips in deionized water for 5S, then soaking the wood chips in a lithium chloride solution at 80 ℃ for 10min, and then swinging and washing the wood chips in the deionized water for 5S.
S6, putting the wood chips treated in the step S5 into a glucose solution with the mass fraction of 50%, heating the wood chips at 80 ℃ for 1h, taking the wood chips out, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
And S7, heating the wood chips treated in the step S6 to 900 ℃ at a speed of 2 ℃/min in an argon atmosphere, keeping for 2 hours, and naturally cooling to obtain the carbon-coated lithium phosphide electrode.
Example 3
A preparation method of a carbon-coated lithium phosphide electrode comprises the following specific steps:
s1, cutting off 1500 μm thick wood chips along the direction perpendicular to the fiber direction by a knife and sanding to 600 μm.
S2, the polished wood chips are heated for 2 hours at 80 ℃ by using 1M sodium hydroxide solution and then are washed to be neutral by using deionized water.
S3, heating the wood chips treated in the step S2 at 80 ℃ for 2h by using 1M hydrochloric acid solution, washing the wood chips to be neutral by using deionized water, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
S4, preparing 0.3M phosphoric acid solution and preparing 3 times of lithium chloride solution with the concentration of the phosphoric acid solution.
S5, soaking the wood chips obtained in the step S3 in a phosphoric acid solution at 80 ℃ for 10min, then swinging and washing the wood chips in deionized water for 5S, then soaking the wood chips in a lithium chloride solution at 80 ℃ for 10min, then swinging and washing the wood chips in deionized water for 5S, and repeating the step for 30 times.
S6, putting the wood chips treated in the step S5 into a glucose solution with the mass fraction of 50%, heating the wood chips at 80 ℃ for 1h, taking the wood chips out, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
And S7, heating the wood chips treated in the step S6 to 800 ℃ at a speed of 2 ℃/min in an argon atmosphere, keeping for 2 hours, and naturally cooling to obtain the carbon-coated lithium phosphide electrode.
Example 4
A preparation method of a carbon-coated lithium phosphide electrode comprises the following specific steps:
s1, cutting off 1500 μm thick wood chips along the direction perpendicular to the fiber direction by a knife and sanding to 700 μm.
S2, the polished wood chips are heated for 2 hours at 80 ℃ by using 1M sodium hydroxide solution and then are washed to be neutral by using deionized water.
S3, heating the wood chips treated in the step S2 at 80 ℃ for 2h by using 1M hydrochloric acid solution, washing the wood chips to be neutral by using deionized water, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
S4, preparing 0.2M phosphoric acid solution and preparing 3 times of lithium chloride solution with the concentration of the phosphoric acid solution.
S5, soaking the wood chips obtained in the step S3 in a phosphoric acid solution at 80 ℃ for 10min, then swinging and washing the wood chips in deionized water for 5S, then soaking the wood chips in a lithium chloride solution at 80 ℃ for 10min, then swinging and washing the wood chips in the deionized water for 5S, and repeating the step for 20 times.
S6, putting the wood chips treated in the step S5 into a glucose solution with the mass fraction of 50%, heating the wood chips at 80 ℃ for 1h, taking the wood chips out, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
And S7, heating the wood chips treated in the step S6 to 700 ℃ at a speed of 2 ℃/min in an argon atmosphere, keeping for 2h, and naturally cooling to obtain the carbon-coated lithium phosphide electrode.
Example 5
A preparation method of a carbon-coated lithium phosphide electrode comprises the following specific steps:
s1, cutting off 1500 μm thick wood chips along the direction perpendicular to the fiber direction by a knife and sanding to 600 μm.
S2, the polished wood chips are heated for 2 hours at 80 ℃ by using 1M sodium hydroxide solution and then are washed to be neutral by using deionized water.
S3, heating the wood chips treated in the step S2 at 80 ℃ for 2h by using 1M hydrochloric acid solution, washing the wood chips to be neutral by using deionized water, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
S4, preparing 0.4M phosphoric acid solution and preparing 3 times of lithium chloride solution with the concentration of the phosphoric acid solution.
S5, soaking the wood chips obtained in the step S3 in a phosphoric acid solution at 80 ℃ for 10min, then swinging and washing the wood chips in deionized water for 5S, then soaking the wood chips in a lithium chloride solution at 80 ℃ for 10min, then swinging and washing the wood chips in the deionized water for 5S, and repeating the step 40 times.
S6, putting the wood chips treated in the step S5 into a glucose solution with the mass fraction of 50%, heating the wood chips at 80 ℃ for 1h, taking the wood chips out, and drying the wood chips in a vacuum drying oven at 100 ℃ for 12 h.
And S7, heating the wood chips treated in the step S6 to 900 ℃ at a speed of 2 ℃/min in an argon atmosphere, keeping for 2 hours, and naturally cooling to obtain the carbon-coated lithium phosphide electrode.
The carbon-coated lithium phosphide electrode obtained in example 1 was subjected to a performance test. The specific test process is as follows: a lithium phosphide electrode is tested by adopting a half-cell, a negative electrode is a lithium sheet, Celgard2325 is used as a diaphragm, LiPF6 with 1M electrolyte is dissolved in a solution of ethylene carbonate, diethyl carbonate and dimethyl carbonate, and the battery is assembled by using an LIR2032 coin-shaped battery case in a glove box which is filled with argon gas for protection and has the humidity and oxygen concentration lower than 1 ppm. In the charge and discharge test system, the charge and discharge test voltage is 0.01-2V; the charging speed is 0.2C; the obtained cyclic capacity curve is shown in figure 1, the specific capacity can reach 963mAh/g, and the capacity is still 883mAh/g after the cycle is performed for 75 times.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A carbon-coated lithium phosphide electrode is characterized in that: comprises a carbon matrix; micron-sized pore channels are arranged on the carbon substrate; lithium phosphide is filled in the micron-sized pore channel; the carbon matrix is obtained by carbonizing wood chips; the micron-sized pore channels are pore channels in the wood chips.
2. The method according to claim 1, wherein the method comprises the steps of: step one, obtaining wood chips with fiber directions parallel to the thickness direction;
step two, heating the wood chips in an alkali solution and an acid solution in sequence;
drying the wood chips, and then sequentially soaking the wood chips in a phosphoric acid solution and a lithium chloride solution to enable the phosphoric acid solution and the lithium chloride solution to enter pores in the wood chips along the fiber direction; soaking the wood chips in a phosphoric acid solution and a lithium chloride solution is carried out once or repeatedly;
step four, heating the wood chips treated in the step three in a glucose solution and then drying;
and step five, heating the wood chips treated in the step four in a dry environment to carbonize the wood chips and glucose, and reacting lithium phosphate with carbon to form lithium phosphide, so as to obtain the carbon-coated lithium phosphide electrode.
3. The method according to claim 2, wherein the method comprises the steps of: the thickness of the wood chip in the first step is 500-800 μm.
4. The method according to claim 2, wherein the method comprises the steps of: the wood chips in the step one are cut by a knife along the direction vertical to the wood fiber and then are ground.
5. The method according to claim 2, wherein the method comprises the steps of: in the second step, the wood chips are heated in an alkali solution and an acid solution and then are respectively washed to be neutral by deionized water; the alkali solution is 1M sodium hydroxide solution; the acid solution was 1M hydrochloric acid solution.
6. The method according to claim 2, wherein the method comprises the steps of: and in the second step, the heating temperature in the alkali solution and the acid solution is both 80 ℃, and the heating time is both 2 h.
7. The method according to claim 2, wherein the method comprises the steps of: in the third step, the molar concentration of the phosphoric acid solution is 0.1-0.5M; the molar concentration of the lithium chloride solution was 3 times that of the phosphoric acid solution.
8. The method according to claim 2, wherein the method comprises the steps of: and in the third step, the wood chips are soaked in the phosphoric acid solution and the lithium chloride solution for 1 to 60 times.
9. The method according to claim 2, wherein the method comprises the steps of: in the fourth step, the mass fraction of the glucose solution is 50%, the heating temperature is 80 ℃, and the heating time is 1 h.
10. The method according to claim 2, wherein the method comprises the steps of: in the fifth step, the wood chips are heated to 700-900 ℃ at the speed of 2 ℃/min in the argon atmosphere, and are naturally cooled after being kept for 2 h.
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| JPH07122261A (en) * | 1993-10-26 | 1995-05-12 | Matsushita Electric Ind Co Ltd | Electrochemical element |
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| US20160217984A1 (en) * | 2013-09-05 | 2016-07-28 | Plansee Se | Conductive target material |
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| JPH07122261A (en) * | 1993-10-26 | 1995-05-12 | Matsushita Electric Ind Co Ltd | Electrochemical element |
| US20160217984A1 (en) * | 2013-09-05 | 2016-07-28 | Plansee Se | Conductive target material |
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