CN115579463A - Graphene lithium iron phosphate composite material, preparation method thereof, pole piece and secondary battery - Google Patents
Graphene lithium iron phosphate composite material, preparation method thereof, pole piece and secondary battery Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 180
- 239000002131 composite material Substances 0.000 title claims abstract description 140
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
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- 239000010439 graphite Substances 0.000 claims abstract description 176
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 146
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The application provides a preparation method of a graphene lithium iron phosphate composite material, which comprises the following steps: uniformly mixing graphite, a dispersing agent, an organic solvent and a lithium salt to obtain graphite slurry; discharging a metal lithium source and the graphite slurry through a container which can be communicated with the anode and the cathode of a power supply to obtain lithium-embedded graphite slurry; drying to obtain lithium-embedded graphite powder, and feeding the lithium-embedded graphite powder into a gas environment in which steam and carbon dioxide are mixed to generate lithium carbonate; rotating and ultrasonically vibrating the graphite powder embedded with the lithium carbonate in deionized water to obtain lithium carbonate composite graphene powder; and preparing the graphene lithium iron phosphate composite material by taking the lithium carbonate composite graphene powder as a lithium source. According to the preparation method, the high-performance graphene lithium iron phosphate composite material can be rapidly prepared, and the recovered graphite material can be adopted, so that the energy is saved, and the performance is improved.
Description
Technical Field
The application relates to the field of battery materials, in particular to a preparation method of a graphene lithium iron phosphate composite material.
Background
The lithium ion battery has the advantages of rapid charge and discharge, no memory effect, high capacity and the like, is the main direction of new energy development, and has become the main material of the power type lithium ion battery due to the advantages of wide raw material source, environmental friendliness, safe use and the like as the lithium iron phosphate is used as the anode material of the lithium ion battery. However, because lithium iron phosphate has low conductivity and energy density, which limits its large-scale application in lithium ion batteries, it is necessary to modify lithium iron phosphate to make it have excellent rate capability and cycle performance.
The existing common modification method is to adopt graphene, and improve the rate capability and the cycle performance of lithium iron phosphate by utilizing the ultra-strong conductivity and the large specific area of the graphene. Graphene is a two-dimensional nanocarbon material consisting of a single layer of carbon atoms in sp 2 The hybrid forms are tightly packed into a honeycomb lattice structure, and have a plurality of excellent performances in the aspects of electricity, heat conductivity, mechanics, optics and the like. At present, the preparation methods of graphene mainly include a micro-mechanical stripping method, a chemical vapor deposition method, an oxidation-reduction method, a solvent stripping method, and a solvothermal method.
The existing graphene preparation method is high in cost, so that the preparation cost of the lithium iron phosphate lithium ion battery positive electrode material is increased. The number of graphene layers prepared by the existing method is large, and can reach dozens of layers or even hundreds of layers, so that the graphene is not beneficial to exerting the modification effect of the graphene on the lithium iron phosphate lithium ion battery anode material.
Disclosure of Invention
It is a primary object of the present application to overcome at least one of the above-mentioned drawbacks of the prior art, and to provide a method for preparing a high-performance graphene lithium iron phosphate composite material rapidly and efficiently.
In order to achieve the purpose, the following technical scheme is adopted in the application:
according to an aspect of the present application, there is provided a method for preparing a graphene lithium iron phosphate composite material, including the steps of:
step 1: preparing graphite slurry: under the protection of dry protective gas, uniformly mixing graphite, a dispersing agent, dimethyl phosphate and lithium hexafluorophosphate to obtain graphite slurry;
and 2, step: preparing lithium intercalation graphite: discharging a metal lithium source and the graphite slurry through a container which can be communicated with the anode and the cathode of a power supply to obtain lithium-embedded graphite slurry;
and 3, step 3: preparing lithium carbonate composite graphene powder: drying the lithium-embedded graphite slurry obtained in the step 2, feeding the dried lithium-embedded graphite slurry into a mixed gas environment containing water vapor and carbon dioxide to react to obtain graphite powder embedded with lithium carbonate, finally obtaining a lithium carbonate composite graphene solution under the action of ultrasound, and filtering and drying the lithium carbonate composite graphene solution to obtain lithium carbonate composite graphene powder;
and 4, step 4: in-situ growth of lithium iron phosphate: and 3, using the lithium carbonate composite graphene powder obtained in the step 3 as a lithium source to prepare the graphene lithium iron phosphate composite material.
According to the preparation method of the graphene lithium iron phosphate composite material, the high-performance graphene and the high-performance lithium iron phosphate lithium ion battery positive electrode material can be prepared through the preparation and in-situ growth of the lithium-intercalated graphite and lithium carbonate composite graphene powder.
According to one embodiment of the present application, the organic solvent in step 1 is one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate; the lithium salt is one or more of lithium hexafluorophosphate, lithium difluoro oxalate borate, lithium fluoro sulfonyl imide and lithium tetrafluoroborate.
According to one embodiment of the present application, the organic solvent in step 1 is dimethyl phosphate and the lithium salt is lithium hexafluorophosphate.
According to one embodiment of the present application, the graphite, the dispersant, the dimethyl phosphate and the lithium hexafluorophosphate in step 1 are mixed in the following molar ratio: graphite: the dispersant is dimethyl phosphate, lithium hexafluorophosphate (30-50) = (2-10): 20-60): 10-20).
In the application, the graphene slurry is prepared according to the above proportion, so that graphite in the prepared graphene slurry can be uniformly dispersed, the lithium ions can be embedded, and the subsequent steps can be performed conveniently.
According to one embodiment of the present application, when the graphite slurry in step 2 changes from black to golden yellow, the intercalation of metallic lithium into graphite is completed.
In the application, by judging the color change of the reactant, the time can be saved on the premise of full reaction, and the production efficiency is improved.
According to one embodiment of the present application, the lithium-intercalated graphite in step 2 may be obtained from the negative electrode of a recycled full-charge lithium ion battery.
In the application, the recycled materials are adopted, so that waste can be avoided, energy is saved, the environment can be protected, and the production cost is reduced.
According to one embodiment of the present application, the molar ratio of lithium to water vapor and carbon dioxide in the lithium-intercalated graphite powder in step 3 is: (10-40): (10-20): (10-40).
In the application, lithium, water vapor and carbon dioxide in a proper proportion are adopted to react to generate required lithium carbonate, a graphite layer is spread, and a foundation is laid for the subsequent preparation of the high-performance lithium iron phosphate lithium ion battery positive electrode material.
According to one embodiment of the present application, step 1 is performed in an atmosphere with a relative humidity < 5%, and step 2 and step 3 are performed in a protective atmosphere.
In the application, the graphite slurry is prepared in the atmosphere with the relative humidity less than 5%, so that the performance of the prepared graphite slurry can be guaranteed. The protection of the protective gas can avoid oxidation in the reaction process and ensure the purity of the generated reactant.
According to one embodiment of the present application, step 4 specifically includes: and (3) uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, spray-drying to obtain mixed powder, adding the lithium carbonate composite graphene powder prepared in the step (3) into the mixed powder, uniformly stirring, and sintering to enable the lithium iron phosphate to grow and crystallize on the surface of graphene in situ to obtain the graphene lithium iron phosphate composite material.
In the application, the mixed powder and the lithium carbonate composite graphene powder are sintered, so that lithium iron phosphate can grow and crystallize on the surface of graphene in situ.
According to one embodiment of the present application, the molar ratio of lithium carbonate, glucose and iron phosphate in step 4 is: (1.05-1.20): (0.1-0.5):1.
In the application, the molar ratio of reactants is limited in the in-situ growth reaction process, and the rate capability and the cycle performance of the grown lithium iron phosphate lithium ion battery anode material can be obviously improved.
According to one embodiment of the application, the molar ratio of the mixed powder material to the lithium carbonate composite graphene powder in the step 4 is as follows: 100: (1-5).
In the application, the ratio of the graphene powder to the lithium iron phosphate cannot be too large or too small, that is, the ratio of the graphene powder to the lithium iron phosphate is in a proper range, too small addition of the graphene can result in crystals with larger particles, and too large addition of the graphene can result in thicker graphene layers on the surfaces of the crystal particles. The rate capability and the cycle performance of the lithium iron phosphate lithium ion battery anode material are not improved.
According to one embodiment of the present application, the sintering temperature in step 4 is 650 ℃ to 950 ℃.
In the application, the sintering temperature is selected to ensure the in-situ growth effect and ensure that the lithium iron phosphate lithium ion battery anode material has stronger electrochemical activity.
According to a second aspect of the present application, there is provided a graphene lithium iron phosphate composite material, wherein a lithium source of a preparation raw material of the composite material comprises the lithium carbonate composite graphene powder obtained in the step 3.
According to a third aspect of the present application, there is provided a positive electrode active material including the graphene lithium iron phosphate composite as described above.
According to the fourth aspect of the present application, a pole piece is provided, the pole piece includes a current collector and an active substance layer, the active substance layer is coated on the current collector, the active substance layer includes the above graphene lithium iron phosphate composite material or the above positive active substance.
According to a fifth aspect of the present application, a lithium ion battery is provided, which includes the above-mentioned pole piece.
According to the technical scheme, the preparation method of the graphene lithium iron phosphate composite material has the advantages and positive effects that:
the preparation method of the graphene lithium iron phosphate composite material comprises the following steps:
step 1: preparing graphite slurry: under the protection of dry protective gas, uniformly mixing graphite, a dispersing agent, an organic solvent and lithium salt to obtain graphite slurry; graphite in the prepared graphene slurry can be uniformly dispersed, and lithium ions can be embedded in the graphene slurry.
And 2, step: preparing lithium intercalation graphite: discharging a metal lithium source and the graphite slurry through a container which can be communicated with the anode and the cathode of a power supply to obtain lithium-embedded graphite slurry;
and step 3: preparing lithium carbonate composite graphene powder: drying the lithium-embedded graphite slurry obtained in the step 2, feeding the dried lithium-embedded graphite slurry into a mixed gas environment containing water vapor and carbon dioxide to react to obtain graphite powder embedded with lithium carbonate, finally obtaining a lithium carbonate composite graphene solution under the action of ultrasound, and filtering and drying the lithium carbonate composite graphene solution to obtain lithium carbonate composite graphene powder; the graphite carbon layer can be fully opened, and the in-situ growth of the lithium iron phosphate is facilitated.
And 4, step 4: in-situ growth of lithium iron phosphate: and 3, preparing the graphene lithium iron phosphate composite material by using the lithium carbonate composite graphene powder obtained in the step 3 as a lithium source. The high-performance lithium iron phosphate lithium ion battery positive electrode material can be obtained, the number of graphene layers is small, and the graphene modification effect on the lithium iron phosphate lithium ion battery positive electrode material is favorably exerted.
According to the preparation method of the graphene lithium iron phosphate composite material, the rate capability and the cycle performance of the lithium iron phosphate lithium ion battery positive electrode material can be remarkably improved through the preparation and in-situ growth of the lithium-intercalated graphite and lithium carbonate composite graphene powder.
Drawings
Various objects, features and advantages of the present application will become more apparent from the following detailed description of preferred embodiments thereof, when considered in conjunction with the accompanying drawings. The drawings are merely exemplary of the application and are not necessarily drawn to scale. In the drawings, like reference characters designate the same or similar parts throughout the different views. Wherein:
fig. 1 is a block diagram of a method for preparing a graphene lithium iron phosphate composite material according to the present application.
FIG. 2 is a schematic representation of the use of an aluminum container in step 2 of the present application.
The reference numerals are illustrated below:
201. an aluminum container;
202. a porous insulating plate;
203. a feed inlet;
204. a discharge port;
205. a matte copper plate;
206. an insulating layer;
A. a graphite slurry;
B. a mixture of metallic lithium.
Detailed Description
Exemplary embodiments that embody features and advantages of the present application are described in detail below in the specification. It is to be understood that the present application is capable of various modifications in various embodiments without departing from the scope of the application, and that the description and drawings are to be taken as illustrative and not restrictive in character.
In the following description of various exemplary embodiments of the present application, reference is made to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration various exemplary structures, systems, and steps in which aspects of the application may be practiced. It is to be understood that other specific arrangements of parts, structures, example devices, systems, and steps may be utilized and structural and functional modifications may be made without departing from the scope of the present application. When introducing elements/components/etc. described and/or illustrated herein, the terms "a," "an," "two," and "three," etc. are used to indicate the presence of one or more elements/components/etc. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements/components/etc. other than the listed elements/components/etc.
As shown in fig. 1 to 2, the preparation method of the graphene lithium iron phosphate composite material of the present application includes the following steps:
step 1: preparing graphite slurry: under the protection of dry protective gas, uniformly mixing graphite, a dispersing agent, an organic solvent and lithium salt to obtain graphite slurry A. Wherein the protective gas may include nitrogen, carbon dioxide, and the like, in addition to inert gases conventional in the art. The dispersant is N-vinyl pyrrolidone (NVP), glycol or polyalcohol.
Step 2: preparing lithium intercalation graphite: and discharging a metal lithium source (metal lithium or a metal lithium mixture) and the graphite slurry through a container (an aluminum container and a wool-faced copper plate) which can be communicated with the anode and the cathode of a power supply to obtain the lithium-embedded graphite slurry.
And step 3: preparing lithium carbonate composite graphene powder: preparing lithium carbonate composite graphene powder: and (3) drying the lithium-embedded graphite slurry obtained in the step (2), sending the dried lithium-embedded graphite slurry into a mixed gas environment containing water vapor and carbon dioxide for reaction to obtain graphite powder embedded with lithium carbonate, finally obtaining a lithium carbonate composite graphene solution under the action of ultrasound, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: and 3, preparing the graphene lithium iron phosphate composite material by using the lithium carbonate composite graphene powder obtained in the step 3 as a lithium source. The high-performance lithium iron phosphate lithium ion battery positive electrode material can be obtained, the number of graphene layers is small, and the graphene modification effect on the lithium iron phosphate lithium ion battery positive electrode material is favorably exerted.
In this embodiment, the organic solvent in step 1 is dimethyl carbonate, and in other embodiments, the organic solvent may also be one or more of diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate.
In this embodiment, the lithium salt is lithium hexafluorophosphate, and in other embodiments, the lithium salt may also be one or more of lithium difluorooxalato borate, lithium fluorosulfonylimide, and lithium tetrafluoroborate.
In this embodiment, step 3 specifically includes: enabling the lithium-intercalated graphite slurry obtained in the step 2 to pass through a drying zone, removing a dispersing agent and dimethyl phosphate to obtain dry lithium-intercalated graphite powder, and then sending the lithium-intercalated graphite powder into a mixed gas environment mixed by steam and carbon dioxide to enable lithium in the lithium-intercalated graphite powder to react with the steam and the carbon dioxide to generate lithium carbonate; then placing the graphite powder embedded with lithium carbonate into deionized water, rotating and ultrasonically vibrating to open the graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder. And 3, the graphite carbon layer can be fully opened, and the in-situ growth of the lithium iron phosphate is facilitated.
In this embodiment, step 4 specifically includes: and (3) uniformly mixing lithium carbonate, glucose and iron phosphate with deionized water, spray-drying to obtain mixed powder, adding the lithium carbonate composite graphene powder prepared in the step (3) into the mixed powder, uniformly stirring, and sintering to enable the lithium iron phosphate to grow and crystallize on the surface of graphene in situ, so as to obtain the graphene lithium iron phosphate composite material.
In this example, the mixing molar ratio of graphite, dispersant, dimethyl phosphate and lithium hexafluorophosphate in step 1 is: graphite: the dispersant is dimethyl phosphate, lithium hexafluorophosphate (30-50), lithium hexafluorophosphate (2-10), lithium hexafluorophosphate (20-60) and lithium hexafluorophosphate (10-20). The graphene slurry is prepared according to the proportion, so that graphite in the prepared graphene slurry can be uniformly dispersed.
In this example, the lithium metal mixture in step 2 refers to a mixture of lithium metal, dimethyl phosphate and lithium hexafluorophosphate. Can avoid the participation of various substances in the preparation process, increase the preparation cost and increase the preparation complexity. Wherein the molar ratio of the metal lithium to the dimethyl phosphate to the lithium hexafluorophosphate is as follows: (2-5): (3-6): (1-3).
In this embodiment, the preparation of the lithium intercalation graphite in step 2 specifically comprises: placing a lithium metal mixture B in an aluminum container 201, wherein two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feed inlet 203, the lower opening is provided with a discharge outlet 204, a matte copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feed inlet 203, then the aluminum container 201 is connected with a positive power supply, the matte copper plate 205 is connected with a negative power supply, and the graphite slurry A and the lithium metal mixture B are discharged to enable lithium metal to be embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow, thereby obtaining the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
In this example, the lithium-intercalated graphite in step 2 may be obtained from the negative electrode of a recovered full-charge lithium ion battery. And by adopting recycled materials, waste can be avoided, energy is saved, and production cost is reduced.
In this embodiment, the molar ratio of lithium to water vapor and carbon dioxide in the lithium-intercalated graphite powder in step 3 is: (10-40): (10-20): (10-40). Lithium, water vapor and carbon dioxide in a proper proportion are adopted to react to generate the required lithium carbonate, so that the graphite layer is fully expanded.
In this example, step 1 was carried out in an atmosphere with a relative humidity of < 5%, and steps 2 and 3 were carried out in a protective gas atmosphere. Wherein the protective gas may include nitrogen, carbon dioxide, and the like, in addition to inert gases conventional in the art. Oxidation during the reaction can be avoided.
In this example, the molar ratio of lithium carbonate, glucose and iron phosphate in step 4 is: (1.05-1.20): (0.1-0.5):1. The rate capability and the cycle performance of the grown lithium iron phosphate lithium ion battery anode material can be improved, and the alternating current impedance is reduced.
In this embodiment, the molar ratio of the mixed powder material to the lithium carbonate composite graphene powder in step 4 is as follows: 100: (1-5). Too little graphene addition results in crystals with larger particles, and too much addition results in thicker graphene layers on the surface of the grains.
In this embodiment, the sintering temperature in step 4 is 650 ℃ to 950 ℃. Not only can make the material have stronger crystallinity, but also can avoid the crystal agglomeration.
It should be noted herein that the methods of preparing the lithium iron graphene phosphate composite shown in the drawings and described in the present specification are only a few examples that can employ the principles of the present application. It should be clearly understood that the principles of the present application are in no way limited to any details of the method of preparing the graphene lithium iron phosphate composite shown in the drawings or described in the present specification.
For a further understanding of the content of the present application, reference will now be made in detail to the present application with reference to specific embodiments. It should be noted that, for reasons of space, only some of the examples are listed below, wherein the parameters and the like in the preparation are not limited to the specific examples described below.
Example one
Step 1: preparing graphite slurry: uniformly mixing graphite, N-vinyl pyrrolidone (NVP), dimethyl phosphate and lithium hexafluorophosphate under the protection of nitrogen with the relative humidity of less than 5%, wherein the graphite comprises N-vinyl pyrrolidone (NVP), dimethyl phosphate, lithium hexafluorophosphate = 35;
step 2: preparing lithium intercalation graphite: placing a metal lithium mixture B in an aluminum container 201, wherein the metal lithium mixture B refers to a mixture of metal lithium, dimethyl phosphate and lithium hexafluorophosphate, and the molar ratio of the metal lithium, the dimethyl phosphate and the lithium hexafluorophosphate is: 2:3:3. Two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feeding hole 203, the lower opening is provided with a discharging hole 204, a rough-surface copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feeding hole 203, then the aluminum container 201 is connected with a power supply anode, the rough-surface copper plate 205 is connected with the power supply cathode, and the graphite slurry A and a metal lithium mixture B are discharged, so that metal lithium is embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow to obtain the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
And step 3: preparing lithium carbonate composite graphene powder: and (3) removing N-vinyl pyrrolidone (NVP) and dimethyl phosphate from the lithium-intercalated graphite slurry obtained in the step (2) through a drying zone to obtain dry lithium-intercalated graphite powder, and then feeding the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide, wherein the proportion of lithium, the water vapor and the carbon dioxide in the lithium-intercalated graphite powder is as follows: 10:15:18. So that lithium in the lithium-embedded graphite powder reacts with water vapor and carbon dioxide to generate lithium carbonate; then placing the graphite powder embedded with lithium carbonate into deionized water, rotating and ultrasonically vibrating to open the graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, wherein the molar ratio of the lithium carbonate to the glucose to the iron phosphate is as follows: 1.05: 100, uniformly stirring, and then sintering, wherein the sintering temperature is 650 ℃, so that the lithium iron phosphate grows and crystallizes on the surface of the graphene in situ to obtain the graphene lithium iron phosphate composite material.
Example two
Step 1: preparing graphite slurry: uniformly mixing graphite, ethylene glycol, dimethyl phosphate and lithium hexafluorophosphate under the protection of nitrogen with relative humidity of less than 5%, wherein the ratio of graphite to ethylene glycol to dimethyl phosphate to lithium hexafluorophosphate = 40;
step 2: preparing lithium intercalation graphite: placing a metal lithium mixture B in an aluminum container 201, wherein the metal lithium mixture B refers to a mixture of metal lithium, dimethyl phosphate and lithium hexafluorophosphate, and the molar ratio of the metal lithium, the dimethyl phosphate and the lithium hexafluorophosphate is as follows: 4:6:3. Two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feeding hole 203, the lower opening is provided with a discharging hole 204, a rough-surface copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feeding hole 203, then the aluminum container 201 is powered on, the rough-surface copper plate 205 is powered on, a negative electrode is powered on, and the graphite slurry A and a metal lithium mixture B are discharged so that metal lithium is embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow to obtain the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
And 3, step 3: preparing lithium carbonate composite graphene powder: and (3) allowing the lithium-intercalated graphite slurry obtained in the step (2) to pass through a drying zone, removing ethylene glycol and dimethyl phosphate to obtain dry lithium-intercalated graphite powder, and then conveying the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide, wherein the proportion of lithium in the lithium-intercalated graphite powder to the water vapor and the carbon dioxide is as follows: 15:16:35. So that lithium in the lithium-embedded graphite powder reacts with water vapor and carbon dioxide to generate lithium carbonate; then placing the graphite powder embedded with lithium carbonate into deionized water, rotating and ultrasonically vibrating to open the graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, wherein the molar ratio of the lithium carbonate to the glucose to the iron phosphate is as follows: 1.1: and (2) stirring uniformly, and then sintering at the sintering temperature of 700 ℃, so that the lithium iron phosphate grows and crystallizes on the surface of the graphene in situ to obtain the graphene lithium iron phosphate composite material.
EXAMPLE III
Step 1: preparing graphite slurry: uniformly mixing graphite, trimethylolethane, diethyl phosphate and lithium difluorooxalato borate under the protection of nitrogen with the relative humidity of less than 5%, wherein the ratio of graphite to trimethylolethane to diethyl phosphate to lithium difluorooxalato borate = 30;
step 2: preparing lithium intercalation graphite: placing a metal lithium mixture B in an aluminum container 201, wherein the metal lithium mixture B refers to a mixture of metal lithium, diethyl phosphate and lithium difluorooxalato borate, and the molar ratio of the metal lithium, the diethyl phosphate and the lithium difluorooxalato borate is as follows: 5:6:6. Two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feeding hole 203, the lower opening is provided with a discharging hole 204, a rough-surface copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feeding hole 203, then the aluminum container 201 is connected with a power supply anode, the rough-surface copper plate 205 is connected with the power supply cathode, and the graphite slurry A and a metal lithium mixture B are discharged, so that metal lithium is embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow to obtain the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
And step 3: preparing lithium carbonate composite graphene powder: and (3) allowing the lithium-intercalated graphite slurry obtained in the step (2) to pass through a drying area to remove trimethylolethane and diethyl phosphate to obtain dry lithium-intercalated graphite powder, and then conveying the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide, wherein the proportion of lithium in the lithium-intercalated graphite powder to the water vapor and the carbon dioxide is as follows: 19:13:38. So that lithium in the lithium-embedded graphite powder reacts with water vapor and carbon dioxide to generate lithium carbonate; then placing the graphite powder embedded with lithium carbonate into deionized water, rotating and ultrasonically vibrating to open the graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, wherein the molar ratio of the lithium carbonate to the glucose to the iron phosphate is as follows: 1.15, after spray drying, obtaining a mixed powder material, and adding the lithium carbonate composite graphene powder prepared in the step 3 into the mixed powder material, wherein the molar ratio of the mixed powder material to the lithium carbonate composite graphene powder is as follows: and (3) stirring uniformly, and then sintering at the sintering temperature of 750 ℃ to enable the lithium iron phosphate to grow and crystallize in situ on the surface of the graphene, so as to obtain the graphene lithium iron phosphate composite material.
Example four
Step 1: preparing graphite slurry: uniformly mixing graphite, xylitol, dimethyl phosphate and lithium hexafluorophosphate under the protection of nitrogen with the relative humidity of less than 5%, wherein the ratio of graphite to xylitol to dimethyl phosphate to lithium hexafluorophosphate = 45;
step 2: preparing lithium intercalation graphite: placing a metal lithium mixture B in an aluminum container 201, wherein the metal lithium mixture B refers to a mixture of metal lithium, dimethyl phosphate and lithium hexafluorophosphate, and the molar ratio of the metal lithium, the dimethyl phosphate and the lithium hexafluorophosphate is as follows: 4.5:5.5:4.8. Two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feeding hole 203, the lower opening is provided with a discharging hole 204, a rough-surface copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feeding hole 203, then the aluminum container 201 is powered on, the rough-surface copper plate 205 is powered on, a negative electrode is powered on, and the graphite slurry A and a metal lithium mixture B are discharged so that metal lithium is embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow to obtain the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
And step 3: preparing lithium carbonate composite graphene powder: and (3) allowing the lithium-intercalated graphite slurry obtained in the step (2) to pass through a drying zone to remove xylitol and dimethyl phosphate to obtain dry lithium-intercalated graphite powder, and then conveying the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide, wherein the proportion of lithium in the lithium-intercalated graphite powder to the water vapor and the carbon dioxide is as follows: 21:15:35. So that lithium in the lithium-embedded graphite powder reacts with water vapor and carbon dioxide to generate lithium carbonate; and then placing the graphite powder embedded with lithium carbonate in deionized water, rotating and ultrasonically vibrating to open a graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, wherein the molar ratio of the lithium carbonate to the glucose to the iron phosphate is as follows: 1.18, 0.5, after spray drying, obtaining a mixed powder material, and adding the lithium carbonate composite graphene powder prepared in the step 3 into the mixed powder material, wherein the molar ratio of the mixed powder material to the lithium carbonate composite graphene powder is as follows: and (5) stirring uniformly, and then sintering at the temperature of 800 ℃ to enable the lithium iron phosphate to grow and crystallize in situ on the surface of the graphene, so as to obtain the graphene lithium iron phosphate composite material.
EXAMPLE five
Step 1: preparing graphite slurry: uniformly mixing graphite, glycerol, dimethyl phosphate and lithium hexafluorophosphate under the protection of nitrogen with the relative humidity of less than 5%, wherein the ratio of graphite to glycerol to dimethyl phosphate to lithium hexafluorophosphate =30: 48, to obtain graphite slurry a;
step 2: preparing lithium intercalation graphite: placing a metal lithium mixture B in an aluminum container 201, wherein the metal lithium mixture B refers to a mixture of metal lithium, dimethyl phosphate and lithium hexafluorophosphate, and the molar ratio of the metal lithium, the dimethyl phosphate and the lithium hexafluorophosphate is as follows: 3:5:6. Two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feeding hole 203, the lower opening is provided with a discharging hole 204, a rough-surface copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feeding hole 203, then the aluminum container 201 is connected with a power supply anode, the rough-surface copper plate 205 is connected with the power supply cathode, and the graphite slurry A and a metal lithium mixture B are discharged, so that metal lithium is embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow, thereby obtaining the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
And step 3: preparing lithium carbonate composite graphene powder: and (3) allowing the lithium-intercalated graphite slurry obtained in the step (2) to pass through a drying zone to remove glycerol and dimethyl phosphate to obtain dry lithium-intercalated graphite powder, and then conveying the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide, wherein the proportion of lithium, the water vapor and the carbon dioxide in the lithium-intercalated graphite powder is as follows: 40:16:35. So that lithium in the lithium-embedded graphite powder reacts with water vapor and carbon dioxide to generate lithium carbonate; then placing the graphite powder embedded with lithium carbonate into deionized water, rotating and ultrasonically vibrating to open the graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, wherein the molar ratio of the lithium carbonate to the glucose to the iron phosphate is as follows: 1.18: 100.5, uniformly stirring, and then sintering, wherein the sintering temperature is 850 ℃, so that the lithium iron phosphate grows and crystallizes on the surface of the graphene in situ, thereby obtaining the graphene lithium iron phosphate composite material.
EXAMPLE six
Step 1: preparing graphite slurry: uniformly mixing graphite, pentaerythritol, dimethyl phosphate and lithium hexafluorophosphate under the protection of nitrogen with a relative humidity of < 5%, wherein graphite: pentaerythritol: dimethyl phosphate: lithium hexafluorophosphate = 9;
step 2: preparing lithium intercalation graphite: placing a metal lithium mixture B in an aluminum container 201, wherein the metal lithium mixture B refers to a mixture of metal lithium, dimethyl phosphate and lithium hexafluorophosphate, and the molar ratio of the metal lithium, the dimethyl phosphate and the lithium hexafluorophosphate is as follows: 2:5:4. Two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feeding hole 203, the lower opening is provided with a discharging hole 204, a rough-surface copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feeding hole 203, then the aluminum container 201 is powered on, the rough-surface copper plate 205 is powered on, a negative electrode is powered on, and the graphite slurry A and a metal lithium mixture B are discharged so that metal lithium is embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow, thereby obtaining the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
And 3, step 3: preparing lithium carbonate composite graphene powder: and (3) allowing the lithium-intercalated graphite slurry obtained in the step (2) to pass through a drying zone to remove glycerol and dimethyl phosphate to obtain dry lithium-intercalated graphite powder, and then conveying the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide, wherein the proportion of lithium, the water vapor and the carbon dioxide in the lithium-intercalated graphite powder is as follows: 28:15:40. So that lithium in the lithium-embedded graphite powder reacts with water vapor and carbon dioxide to generate lithium carbonate; then placing the graphite powder embedded with lithium carbonate into deionized water, rotating and ultrasonically vibrating to open the graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, wherein the molar ratio of the lithium carbonate to the glucose to the iron phosphate is as follows: 1.08: 100.5, uniformly stirring, and then sintering, wherein the sintering temperature is 900 ℃, so that the lithium iron phosphate grows and crystallizes on the surface of the graphene in situ to obtain the graphene lithium iron phosphate composite material.
EXAMPLE seven
Step 1: preparing graphite slurry: uniformly mixing graphite, sorbitol, dimethyl phosphate and lithium hexafluorophosphate under the protection of nitrogen with the relative humidity of less than 5%, wherein the ratio of the graphite to sorbitol to dimethyl phosphate to lithium hexafluorophosphate = 50;
step 2: preparing lithium intercalation graphite: placing a metal lithium mixture B in an aluminum container 201, wherein the metal lithium mixture B refers to a mixture of metal lithium, dimethyl phosphate and lithium hexafluorophosphate, and the molar ratio of the metal lithium, the dimethyl phosphate and the lithium hexafluorophosphate is as follows: 1:3:2. Two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feeding hole 203, the lower opening is provided with a discharging hole 204, a rough-surface copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feeding hole 203, then the aluminum container 201 is powered on, the rough-surface copper plate 205 is powered on, a negative electrode is powered on, and the graphite slurry A and a metal lithium mixture B are discharged so that metal lithium is embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow to obtain the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
And step 3: preparing lithium carbonate composite graphene powder: and (3) allowing the lithium-intercalated graphite slurry obtained in the step (2) to pass through a drying zone to remove sorbitol and dimethyl phosphate to obtain dry lithium-intercalated graphite powder, and then conveying the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide, wherein the proportion of lithium in the lithium-intercalated graphite powder to the water vapor and the carbon dioxide is as follows: 24:15:37. So that lithium in the lithium-embedded graphite powder reacts with water vapor and carbon dioxide to generate lithium carbonate; and then placing the graphite powder embedded with lithium carbonate in deionized water, rotating and ultrasonically vibrating to open a graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, wherein the molar ratio of the lithium carbonate to the glucose to the iron phosphate is as follows: 1.08: 100.5, uniformly stirring, and then sintering, wherein the sintering temperature is 950 ℃, so that the lithium iron phosphate grows and crystallizes on the surface of the graphene in situ to obtain the graphene lithium iron phosphate composite material.
Example eight
Step 1: preparing graphite slurry: under the protection of nitrogen with the relative humidity of less than 5%, uniformly mixing graphite, sorbitol, ethylene carbonate and lithium fluorosulfonylimide, wherein the ratio of the graphite to the sorbitol to the ethylene carbonate to the lithium fluorosulfonylimide is = 16, so as to obtain graphite slurry A;
step 2: preparing lithium intercalation graphite: placing a metal lithium mixture B in an aluminum container 201, wherein the metal lithium mixture B refers to a mixture of metal lithium, ethylene carbonate and lithium fluorosulfonylimide, and the molar ratio of the metal lithium, the ethylene carbonate and the lithium fluorosulfonylimide is as follows: 1:3:2. Two aluminum containers 201 are arranged at intervals, two porous insulating plates 202 are arranged on opposite side surfaces of the two aluminum containers 201, a cavity with an upper opening and a lower opening is formed between the two porous insulating plates 202, the upper opening is provided with a feeding hole 203, the lower opening is provided with a discharging hole 204, a rough-surface copper plate 205 is arranged in the cavity and is parallel to the two porous insulating plates 202, the graphite slurry A prepared in the step 1 is fed from the feeding hole 203, then the aluminum container 201 is connected with a power supply anode, the rough-surface copper plate 205 is connected with the power supply cathode, and the graphite slurry A and a metal lithium mixture B are discharged, so that metal lithium is embedded into graphite; and completing the intercalation when the color of the graphite is changed from black to golden yellow, thereby obtaining the lithium-intercalated graphite slurry. The lithium metal mixture B in this step may also be lithium metal.
And 3, step 3: preparing lithium carbonate composite graphene powder: and (3) allowing the lithium-intercalated graphite slurry obtained in the step (2) to pass through a drying zone, removing sorbitol and ethylene carbonate to obtain dried lithium-intercalated graphite powder, and then conveying the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide, wherein the proportion of lithium in the lithium-intercalated graphite powder to the water vapor and the carbon dioxide is as follows: 28:15:37. So that lithium in the lithium-embedded graphite powder reacts with water vapor and carbon dioxide to generate lithium carbonate; then placing the graphite powder embedded with lithium carbonate into deionized water, rotating and ultrasonically vibrating to open the graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain the lithium carbonate composite graphene powder.
And 4, step 4: in-situ growth of lithium iron phosphate: uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, wherein the molar ratio of the lithium carbonate to the glucose to the iron phosphate is as follows: 1.07: 100, uniformly stirring, and then sintering, wherein the sintering temperature is 950 ℃, so that the lithium iron phosphate grows and crystallizes on the surface of the graphene in situ to obtain the graphene lithium iron phosphate composite material.
The lithium intercalation graphite in the above examples may be obtained from the negative electrode of a recovered full-charge lithium ion battery. And by adopting the recycled materials, waste can be avoided, and the production cost is reduced.
The above presents various embodiments, or examples, in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the application. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value and should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
According to the preparation method of the graphene lithium iron phosphate composite material, the prepared graphene lithium iron phosphate composite material is used as a lithium ion battery anode material, when the multiplying power is 0.1C, the specific capacity of initial discharge is 160.5mAh/g, and after 8 times of circulation, the specific discharge capacity can reach 162.5mAh/g. When the capacity factor is 1C, the first discharge specific capacity is 151.3mAh/g, the capacity retention rate is 99.7 percent after 10 cycles, and the capacity attenuation is very small. Under the multiplying power of 5C and 20C, the discharge specific capacities are respectively 130.8 and 98.6mAh/g. Can still reach higher specific discharge capacity under the high rate. The data show that the lithium iron phosphate lithium ion battery positive electrode material prepared by the method has excellent rate performance and cycle performance, can greatly improve the discharge capacity of the battery, and remarkably improves the service efficiency.
To sum up, the preparation method of the graphene lithium iron phosphate composite material comprises the following steps:
step 1: preparing graphite slurry: under the protection of dry protective gas, uniformly mixing graphite, a dispersing agent, an organic solvent and lithium salt to obtain graphite slurry; graphite in the prepared graphene slurry can be uniformly dispersed, and lithium ions can be embedded in the graphene slurry.
And 2, step: preparing lithium intercalation graphite: placing a metal lithium source in a container (aluminum container) which can be communicated with the positive electrode and the negative electrode of a power supply, wherein the aluminum container is provided with two porous insulation plates which are arranged at intervals, two opposite side surfaces of the two aluminum containers are provided with two porous insulation plates, an upper opening and a lower opening are formed between the two porous insulation plates, the upper opening is provided with a feed inlet, the lower opening is provided with a discharge outlet, a matte copper plate is arranged in the cavity and is parallel to the two porous insulation plates, the graphite slurry prepared in the step 1 is fed from the feed inlet, then the aluminum container is connected with the positive electrode of the power supply, the matte copper plate is connected with the negative electrode of the power supply, and the graphite slurry and the metal lithium or the metal lithium mixture are discharged to enable the metal lithium to be embedded into graphite; after the intercalation is finished, obtaining lithium intercalation graphite slurry; lithium ions can be fully inserted into the graphite.
And step 3: preparing lithium carbonate composite graphene powder: enabling the lithium-intercalated graphite slurry obtained in the step 2 to pass through a drying zone, removing a dispersing agent and an organic solvent to obtain dry lithium-intercalated graphite powder, and then sending the lithium-intercalated graphite powder into a mixed gas environment mixed by water vapor and carbon dioxide to enable lithium in the lithium-intercalated graphite powder to react with the water vapor and the carbon dioxide to generate lithium carbonate; then placing the graphite powder embedded with lithium carbonate in deionized water, rotating and ultrasonically vibrating to open a graphite carbon layer to obtain a lithium carbonate composite graphene solution, and filtering and drying the lithium carbonate composite graphene solution to obtain lithium carbonate composite graphene powder; the graphite carbon layer can be fully opened, and the in-situ growth of the lithium iron phosphate is facilitated.
And 4, step 4: in-situ growth of lithium iron phosphate: and (3) uniformly mixing lithium carbonate, glucose and iron phosphate with deionized water, spray-drying to obtain mixed powder, adding the lithium carbonate composite graphene powder prepared in the step (3) into the mixed powder, uniformly stirring, and sintering to enable the lithium iron phosphate to grow and crystallize on the surface of graphene in situ, so as to obtain the graphene lithium iron phosphate composite material. The high-performance lithium iron phosphate lithium ion battery positive electrode material can be obtained, the number of graphene layers is small, and the graphene modification effect on the lithium iron phosphate lithium ion battery positive electrode material is favorably exerted.
According to the preparation method of the graphene lithium iron phosphate composite material, the rate performance and the cycle performance of the lithium iron phosphate lithium ion battery anode material can be remarkably improved through the preparation and in-situ growth of the lithium-embedded graphite and lithium carbonate composite graphene powder, the service efficiency of the battery is improved, and the service life of the battery is prolonged.
According to the graphene lithium iron phosphate composite material provided by the application, the lithium source of the preparation raw material of the composite material comprises the lithium carbonate composite graphene powder obtained in the step 3.
The positive active material provided by the application comprises the graphene lithium iron phosphate composite material.
The application provides a pole piece, pole piece include mass flow body and active substance layer, active substance layer coat in on the mass flow body, the active substance layer includes foretell graphite alkene lithium iron phosphate combined material or foretell positive pole active material.
The lithium ion battery provided by the application comprises the pole piece.
Exemplary embodiments of methods of preparing the lithium iron graphene phosphate composite material set forth herein are described and/or illustrated in detail above. The embodiments of the present application are not limited to the specific embodiments described herein, but rather, components and/or steps of each embodiment may be utilized independently and separately from other components and/or steps described herein. Each component and/or step of one embodiment can also be used in combination with other components and/or steps of other embodiments. When introducing elements/components/etc. described and/or illustrated herein, the articles "a," "an," and "the" are intended to mean that there are one or more of the elements/components/etc. The terms "comprising," "including," and "having" are intended to be inclusive and mean that there may be additional elements/components/etc. other than the listed elements/components/etc. The terms "upper", "lower", "left", "right", "front", "rear", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing embodiments of the present invention and simplifying the description, but do not indicate or imply that the referred devices or units must have a specific direction, be configured in a specific orientation, and operate, and thus, should not be construed as limiting the embodiments of the present invention.
The embodiments of the present application are not limited to the specific embodiments described herein, but rather, components of each embodiment may be utilized independently and separately from other components described herein. Each component of one embodiment can also be used in combination with other components of other embodiments. In the description herein, reference to the term "one embodiment," "some embodiments," "other embodiments," or the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the embodiments. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above description is only a preferred embodiment of the claimed embodiments and is not intended to limit the claimed embodiments, and various modifications and changes may be made to the claimed embodiments by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the applied embodiment shall be included in the protection scope of the applied embodiment.
Claims (16)
1. The preparation method of the graphene lithium iron phosphate composite material is characterized by comprising the following steps of:
step 1: preparing graphite slurry: under the protection of dry protective gas, uniformly mixing graphite, a dispersing agent, an organic solvent and lithium salt to obtain graphite slurry;
step 2: preparing lithium intercalation graphite: discharging a metal lithium source and the graphite slurry through a container which can be communicated with the anode and the cathode of a power supply, so that metal lithium is embedded into graphite, and obtaining lithium-embedded graphite slurry after the embedding is finished;
and step 3: preparing lithium carbonate composite graphene powder: drying the lithium-embedded graphite slurry obtained in the step 2, feeding the dried lithium-embedded graphite slurry into a mixed gas environment containing water vapor and carbon dioxide to react to obtain graphite powder embedded with lithium carbonate, finally obtaining a lithium carbonate composite graphene solution under the action of ultrasound, and filtering and drying the lithium carbonate composite graphene solution to obtain lithium carbonate composite graphene powder;
and 4, step 4: in-situ growth of lithium iron phosphate: and 3, preparing the graphene lithium iron phosphate composite material by using the lithium carbonate composite graphene powder obtained in the step 3 as a lithium source.
2. The method for preparing the graphene lithium iron phosphate composite material according to claim 1, wherein the organic solvent in step 1 is one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate; the lithium salt is one or more of lithium hexafluorophosphate, lithium difluoro oxalate borate, lithium fluoro sulfonyl imide and lithium tetrafluoroborate.
3. The method for preparing the graphene lithium iron phosphate composite according to claim 2, wherein the organic solvent in the step 1 is dimethyl phosphate and the lithium salt is lithium hexafluorophosphate.
4. The method for preparing the graphene lithium iron phosphate composite material according to claim 3, wherein the graphite, the dispersant, the dimethyl phosphate and the lithium hexafluorophosphate in the step 1 are mixed in a molar ratio of: graphite: the dispersant is dimethyl phosphate, lithium hexafluorophosphate (30-50) = (2-10): 20-60): 10-20).
5. The method for preparing the lithium iron phosphate graphene composite material according to claim 1, wherein the intercalation of lithium metal into graphite is completed when the graphite slurry in the step 2 changes from black to golden yellow.
6. The method for preparing the lithium iron phosphate graphene composite material according to claim 1, wherein the lithium-intercalated graphite slurry in the step 2 is obtained from a negative electrode of a recycled full-power lithium ion battery.
7. The method for preparing the lithium iron phosphate graphene composite material according to claim 1, wherein the molar ratio of lithium to water vapor and carbon dioxide in the lithium-intercalated graphite powder in the step 3 is as follows: (10-40): (10-20): (10-40).
8. The method for preparing the lithium iron phosphate graphene composite material according to claim 1, wherein step 1 is performed in an atmosphere with a relative humidity of less than 5%, and steps 2 and 3 are performed in a protective gas.
9. The method for preparing the graphene lithium iron phosphate composite material according to claim 5, wherein the step 4 specifically comprises: and (3) uniformly mixing lithium carbonate, glucose and deionized water for iron phosphate, spray-drying to obtain mixed powder, adding the lithium carbonate composite graphene powder prepared in the step (3) into the mixed powder, uniformly stirring, and sintering to enable the lithium iron phosphate to grow and crystallize on the surface of graphene in situ to obtain the graphene lithium iron phosphate composite material.
10. The method for preparing the graphene lithium iron phosphate composite material according to claim 9, wherein the molar ratio of lithium carbonate, glucose and iron phosphate is as follows: (1.05-1.20): (0.1-0.5):1.
11. The method for preparing the graphene lithium iron phosphate composite material according to claim 9, wherein the molar ratio of the mixed powder material to the lithium carbonate composite graphene powder in the step 4 is: 100: (1-5).
12. The method for preparing the lithium iron phosphate graphene composite material according to claim 9, wherein the sintering temperature in the step 4 is 650 ℃ to 950 ℃.
13. A graphene lithium iron phosphate composite material, wherein a lithium source of a preparation raw material of the composite material comprises the lithium carbonate composite graphene powder obtained in step 3 according to any one of claims 1 to 12.
14. A positive electrode active material, comprising the graphene lithium iron phosphate composite according to claim 13.
15. A pole piece, comprising a current collector and an active material layer coated on the current collector, wherein the active material layer comprises the graphene lithium iron phosphate composite material according to claim 13 or the positive active material according to claim 14.
16. A lithium ion battery comprising the pole piece of claim 15.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530930A (en) * | 2011-09-05 | 2012-07-04 | 东莞新能源科技有限公司 | Method for preparing graphene by electrochemical stripping |
| CN103094573A (en) * | 2013-01-17 | 2013-05-08 | 东莞新能源科技有限公司 | Preparation method of silicon-based/graphene composite |
| CN103259062A (en) * | 2013-04-17 | 2013-08-21 | 清华大学深圳研究生院 | Method for regenerating graphene by recovering waste lithium ion battery |
| CN103311551A (en) * | 2013-06-04 | 2013-09-18 | 成都银鑫新能源有限公司 | Negative material of lithium-ion battery and preparation method thereof |
| CN104058395A (en) * | 2014-07-11 | 2014-09-24 | 武汉理工大学 | Method for preparing graphene by carrying out ultrasonic treatment on lithium intercalated graphite |
| CN106207302A (en) * | 2016-08-12 | 2016-12-07 | 合肥国轩高科动力能源有限公司 | Method for recovering anode material of waste lithium ion battery |
| CN106711447A (en) * | 2016-12-19 | 2017-05-24 | 重庆汉岳科技发展有限公司 | Preparation method of compound graphene lithium battery positive electrode material |
| CN109256547A (en) * | 2018-09-05 | 2019-01-22 | 合肥国轩电池材料有限公司 | A kind of preparation method of porous graphene-lithium iron phosphate positive material |
| CN110085809A (en) * | 2018-01-25 | 2019-08-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene nano tape base composite ferric lithium phosphate material, preparation method and application |
| CN111252757A (en) * | 2019-10-10 | 2020-06-09 | 中国科学院生态环境研究中心 | Method for preparing graphene by using waste lithium ion power battery |
| CN113437378A (en) * | 2021-06-17 | 2021-09-24 | 华南理工大学 | Method for recycling and reusing anode and cathode of waste battery |
| CN114824214A (en) * | 2022-04-25 | 2022-07-29 | 广东墨睿科技有限公司 | Preparation method of multilayer coated high-nickel ternary material |
-
2022
- 2022-08-17 CN CN202210988254.3A patent/CN115579463B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102530930A (en) * | 2011-09-05 | 2012-07-04 | 东莞新能源科技有限公司 | Method for preparing graphene by electrochemical stripping |
| CN103094573A (en) * | 2013-01-17 | 2013-05-08 | 东莞新能源科技有限公司 | Preparation method of silicon-based/graphene composite |
| CN103259062A (en) * | 2013-04-17 | 2013-08-21 | 清华大学深圳研究生院 | Method for regenerating graphene by recovering waste lithium ion battery |
| CN103311551A (en) * | 2013-06-04 | 2013-09-18 | 成都银鑫新能源有限公司 | Negative material of lithium-ion battery and preparation method thereof |
| CN104058395A (en) * | 2014-07-11 | 2014-09-24 | 武汉理工大学 | Method for preparing graphene by carrying out ultrasonic treatment on lithium intercalated graphite |
| CN106207302A (en) * | 2016-08-12 | 2016-12-07 | 合肥国轩高科动力能源有限公司 | Method for recovering anode material of waste lithium ion battery |
| CN106711447A (en) * | 2016-12-19 | 2017-05-24 | 重庆汉岳科技发展有限公司 | Preparation method of compound graphene lithium battery positive electrode material |
| CN110085809A (en) * | 2018-01-25 | 2019-08-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Graphene nano tape base composite ferric lithium phosphate material, preparation method and application |
| CN109256547A (en) * | 2018-09-05 | 2019-01-22 | 合肥国轩电池材料有限公司 | A kind of preparation method of porous graphene-lithium iron phosphate positive material |
| CN111252757A (en) * | 2019-10-10 | 2020-06-09 | 中国科学院生态环境研究中心 | Method for preparing graphene by using waste lithium ion power battery |
| CN113437378A (en) * | 2021-06-17 | 2021-09-24 | 华南理工大学 | Method for recycling and reusing anode and cathode of waste battery |
| CN114824214A (en) * | 2022-04-25 | 2022-07-29 | 广东墨睿科技有限公司 | Preparation method of multilayer coated high-nickel ternary material |
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