CN112614984B - Graphite negative electrode material of low-magnetism substance for lithium battery and preparation method thereof - Google Patents
Graphite negative electrode material of low-magnetism substance for lithium battery and preparation method thereof Download PDFInfo
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- CN112614984B CN112614984B CN202011556893.XA CN202011556893A CN112614984B CN 112614984 B CN112614984 B CN 112614984B CN 202011556893 A CN202011556893 A CN 202011556893A CN 112614984 B CN112614984 B CN 112614984B
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B25/00—Details of general application not covered by group F26B21/00 or F26B23/00
- F26B25/06—Chambers, containers, or receptacles
- F26B25/066—Movable chambers, e.g. collapsible, demountable
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F26—DRYING
- F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
- F26B5/00—Drying solid materials or objects by processes not involving the application of heat
- F26B5/04—Drying solid materials or objects by processes not involving the application of heat by evaporation or sublimation of moisture under reduced pressure, e.g. in a vacuum
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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 graphite negative electrode material comprises 90-110 parts of a graphite main body material, 10-50 parts of a carbonization material, 5-10 parts of a binder, 1-5 parts of a surfactant and 1-500 parts of water, wherein the carbonization material is prepared from at least one of needle coke and asphalt coke through high-temperature reaction and heat preservation magnetization. The application also provides a preparation method which comprises the following steps: (1) Placing the carbonized material in a shearing mixer with the vibration frequency of 10 to 15Hz for stirring; (2) adding an adhesive, and mixing materials with the vibration frequency of 15 to 25Hz; (3) mixing materials with the vibration frequency of 10 to 15Hz; (4) Adding a surfactant and water, stirring at high frequency until the viscosity reaches the standard, adding an adhesive, stirring at low frequency, and uniformly mixing; (5) And (3) coating the copper foil, and then sending the copper foil into a drying oven for drying to obtain the graphite negative plate for the lithium battery. The carbonized material overcomes the defects of low tap density of the graphite main material and unstable cathode material caused by the lamella of the mesophase structure, and reduces the accident probability by matching with the modified drying box.
Description
Technical Field
The invention belongs to the technical field of graphite material preparation, and particularly relates to a graphite negative electrode material of a low-magnetic substance for a lithium battery and a preparation method thereof.
Background
The lithium ion battery mainly comprises a positive electrode, a negative electrode, an electrolyte capable of conducting lithium ions and a diaphragm for separating the positive electrode from the negative electrode. The lithium ion battery negative electrode materials are divided into the following categories: carbon material negative electrodes (including graphitic carbon materials, non-graphitic carbon materials, doped carbon materials, coated carbon materials), non-carbon negative electrodes (including alloy negative electrodes and transition metal oxide negative electrodes). In recent years, lithium ion batteries are widely used in various portable electronic devices, and are gradually applied to new fields such as electric vehicles and large-scale energy storage. These emerging fields put higher demands on the cycle stability, cycle life, high and low temperature performance, and safety of lithium ion batteries. Since the commercialization of lithium ion batteries by sony corporation, carbon materials are the most widely used negative electrode materials for lithium ion batteries. The carbon negative electrode material may be classified into graphitized carbon (natural graphite, artificial graphite) and non-graphitized carbon (soft carbon, hard carbon) according to the structure. Compared with a non-graphitized carbon material, the graphite carbon material has good conductivity and high crystallinity, has a regular crystalline layered structure, carbon atoms are combined in an sp2 hybridization mode, the interlayer spacing is 0.335nm, and are combined by Van der Waals force, and a good layered structure is formed between layers, so that the graphite carbon material is suitable for the intercalation and deintercalation of lithium ions. The theoretical capacity of the graphite material for charging and discharging is 372mAh/g, the lithium intercalation and deintercalation reaction mainly occurs at 0.01-0.25V, and a stable charging and discharging platform is provided.
At present, the preparation of graphite negative electrodes is mainly completed by a direct wet mixing process. CN102208598B discloses an electrode sheet of a graphene coating modified lithium secondary battery and a manufacturing method thereof, the electrode sheet contains an active material layer, when preparing the active material layer, the electrode active material, a conductive additive, a binder and a solvent are weighed according to a ratio, and then fully mixed and dissolved to obtain a slurry, and the slurry is coated on a graphene layer and dried. CN104577040B discloses a preparation method of lithium ion battery cathode slurry, which comprises the steps of firstly weighing deionized water, putting the deionized water into a planetary stirrer barrel, adding CMC, firstly revolving with the planetary stirrer, then adding graphite, a conductive agent and deionized water to freeze ice balls, and finally adding SBR emulsion and stirring to obtain uniformly dispersed lithium ion battery cathode slurry. CN107895776A discloses a method for preparing high-efficiency lithium ion battery slurry, which comprises the steps of adding powdery active material, conductive agent and binder into a stirrer, uniformly stirring, adding solvent into the powdery material for three times, stirring, and finally filtering and discharging by a screen.
In the prior art, although the method of directly adding the solvent, the thickening agent (CMC), the conductive agent, the graphite and other materials in turn into the slurry by stirring and mixing is convenient to process, has longer dispersion time and is suitable for large-scale production. However, for the high-power graphite cathode material, because the material itself has a low tap density, a relatively large specific surface area and contains many functional groups, when the material is processed by a direct wet mixing process, the components in the slurry are difficult to uniformly mix, even agglomerate and delaminate, and in addition, the functional groups on the graphite and other substances are easy to generate side reactions in a long-time dispersion process, and finally, uniform and stable cathode slurry cannot be obtained. Meanwhile, when the cathode slurry is further processed into cathode sheets, due to the high temperature inside the dryer during working, safety accidents such as scalding and the like easily occur to workers during feeding and discharging, and the improvement space is large.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a graphite negative electrode material of a low magnetic substance for a lithium battery and a preparation method thereof, wherein the carbonized material overcomes the disadvantages of low tap density of the graphite main material and instability of the negative electrode material caused by the lamellar structure of an intermediate phase.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a graphite negative electrode material of a low-magnetic substance for a lithium battery comprises the following components in parts by weight: 90 to 110 parts of graphite main body material, 10 to 50 parts of carbonization material, 5 to 10 parts of adhesive, 1 to 5 parts of surfactant and 1 to 500 parts of water, wherein the carbonization material is prepared from at least one of needle coke and asphalt coke through high-temperature reaction, heat preservation and magnetization.
In the design of the scheme, in order to obtain the cathode material with high compaction density, large gram capacity and good cycling stability, the main material is added with the carbonized material, and the carbonized material has the characteristics of structural anisotropy and oriented and ordered arrangement of an intermediate phase structure, so that the carbonized material has the advantages of low thermal expansion coefficient, high density and low crystal expansion, and the defects of low tap density of the graphite main material and instability of the cathode material caused by lamella of the intermediate phase structure can be overcome. The graphite main body material provided by the invention comprises at least one of natural graphite, natural flake graphite, artificial graphite and mesocarbon microbeads, and the particle size of the graphite main body material is 1-50 mu m.
As a further preferred aspect of the present invention, the method for producing the carbonized material comprises: crushing needle coke and/or pitch coke and shaping to obtain crushed material; and (3) putting the crushed material into a carbonization furnace under the conditions of inert gas protection and magnetic field, and carrying out heat preservation reaction at the temperature of 400-440 ℃ for 10-15h to obtain the carbonized material. In order to prevent the mesophase particles of the carbonized material from agglomerating, the inventor adjusts the structure of the carbonized material from large-size carbon microspheres by adjusting the temperature to form a smooth sphere with the minimum surface energy, finally obtains the time which can give the material sufficient mesophase formation by carrying out heat preservation reaction for 10 to 15h within the range of 400 to 440 ℃, and can form the carbonized material with high structural order orientation degree by applying the delocalization treatment of a magnetic field.
As a further preferred aspect of the present invention, there is provided a method for preparing a graphite negative electrode material of a low magnetic substance for a lithium battery, comprising the steps of:
the method comprises the following steps: placing the carbonized material in a shearing mixer with the vibration frequency of 10 to 15Hz for stirring to obtain a mixed powder material;
step two: adding 30-50% by mass of an adhesive into the mixed powder material, and mixing at a vibration frequency of 15-25Hz to obtain a mixture;
step three: adding a graphite main body material into the mixture, and mixing at a frequency of 10 to 15Hz to obtain a coarse material;
step four: adding a surfactant and water into the coarse material, stirring at high frequency until the viscosity reaches the standard, adding the rest of the binder, and stirring at low frequency to mix uniformly to obtain graphite cathode slurry;
step five: and coating the graphite negative electrode slurry on copper foil, and then sending the copper foil into a drying oven for drying to obtain the graphite negative electrode sheet for the lithium battery.
In a further preferred aspect of the present invention, the stirring frequency of the high-frequency stirring is 30 to 40Hz, and the dispersion frequency is 40 to 50Hz; the stirring frequency of the low-frequency stirring is 20 to 30Hz, and the dispersion frequency is 20 to 30Hz.
As a further preferable aspect of the present invention, the drying box in the fifth step includes a box body, an electric heat conduction member disposed in the box body, a material placing plate hinged to an upper end of a first support pillar mounted on a bottom surface of the box body through a first hinge member and located at a lower end of the electric heat conduction member, and a cylinder fixed to an inner bottom surface of the box body and connected to a bottom surface of one side of the material placing plate through a connection member.
As a further preferable aspect of the present invention, the connecting member includes a first connecting member provided with a first groove and connected to the pushing rod of the cylinder, a second connecting member provided in the first groove and screwed to both side walls of the first groove and provided with a second groove through which the pushing rod passes, and a second hinge member connected to an upper end of the second connecting member and connected to a lower surface of the material placing plate.
As a further preferable aspect of the present invention, the lower surface of the first connecting member is further provided with a first channel which is communicated with the first groove and through which the push rod passes, and the push rod is respectively sleeved with a first limit ring located at the lower end of the first channel and a second limit ring located at the upper end of the first channel.
As a further preferable mode of the present invention, the second limiting ring is provided with a connecting rope, one end of the connecting rope is connected to the second limiting ring, and the other end of the connecting rope sequentially penetrates through a second channel which is formed on the side wall of the second connecting member and is communicated with the second groove, a third channel which is formed on the material placing plate, and the connecting rope is connected to a second baffle plate which is arranged on the inner bottom surface of the mounting groove formed at the end of the material placing plate and is connected to the torsion spring member.
As a further preferred aspect of the present invention, a first stopper rod provided to the second baffle is attached to a groove side wall of the mounting groove.
As a further preferred aspect of the present invention, a second stopper rod provided at a lower end of the connection rope is attached to an inner side wall of the box body.
In conclusion, the invention has the following beneficial effects:
in the invention, the defects of low tap density of the graphite main body material and unstable cathode material caused by the lamella of the mesophase structure are overcome by adding the carbonized material into the common graphite main body material.
The carbonized material adopted by the invention is prepared by coke source high-temperature reaction and heat preservation magnetization, and a smooth sphere with the minimum surface energy is formed by adjusting the structure of the large-size carbon microspheres, so that the carbonized material with high structural order orientation degree can be formed.
The drying box is further structurally improved, the lower end of the material placing plate is provided with the hinged support column, the support column is matched with the air cylinder to control the end part of the material placing plate to lift or descend, so that the material placing plate has two modes which are convenient for feeding and discharging and a mode which is parallel to a horizontal line and used for drying, the feed inlet and the discharge outlet are far away from an electric heating element compared with the traditional drying box, and the probability of safety accidents is greatly reduced.
The invention has stable transformation structure of the drying box, is easy to realize and has good application prospect.
Drawings
FIG. 1 is a schematic structural view of a drying box according to the present invention.
Fig. 2 is a schematic structural view of the connector of the present invention.
Fig. 3 is a schematic view of an installation structure of a second baffle plate of the invention.
Fig. 4 is a schematic view of the installation structure of the connection rope of the present invention.
FIG. 5 is a schematic structural view of the connecting member and the second baffle plate when the material placing plate is in the feeding inclined mode.
Fig. 6 is a bottom view of the retainer plate of the present invention.
Detailed Description
Example 1
The embodiment provides a graphite negative electrode material of a low-magnetic substance for a lithium battery, which comprises the following components in parts by weight: 100 parts of graphite host material, 10 parts of carbonized material (obtained by carbonizing pitch coke and needle coke 1.
The preparation method of the carbonized material in the embodiment includes: crushing and shaping needle coke and asphalt coke, mixing the needle coke and the asphalt coke in proportion, and then performing heat preservation reaction for 10 hours in a carbonization furnace under the protection of inert gas and under the condition of applying a magnetic field of 440 ℃ to obtain the carbonized material.
The preparation method of the graphite material in the embodiment is as follows: (1) Stirring the carbonized material in a shearing mixer at the intensity of 10Hz to obtain a mixed powder material; (2) Adding all CMC aqueous solution into the mixed powder material, and adjusting the frequency to be 15Hz to obtain a mixture; (3) Adding a natural graphite material into the obtained mixture, and adjusting the frequency to be 10Hz to obtain a coarse material; (4) Adding a surfactant and water into the obtained coarse material, adding all SBR aqueous solution, continuously stirring at a low frequency of 20Hz and a dispersion frequency of 20Hz, and uniformly mixing to obtain a graphite cathode material after the high-frequency stirring at a high frequency of 30Hz and the dispersion frequency of 40Hz until the viscosity reaches the standard; (5) And coating the obtained graphite negative electrode material on copper foil, and sending the copper foil into a drying oven for vacuum drying at 120 ℃ for 12 hours to prepare the graphite negative electrode sheet for the lithium battery.
The drying cabinet that this embodiment adopted includes: the box 1, upper surface separates a cavity 11 that is used for installing the power through the baffle in the box 1, and the lower surface is provided with the heat insulating board 12 of thickening in the box 1 and prevents that high temperature from overflowing, is provided with feed inlet and discharge gate (not marked in the figure) respectively in the left and right sides of box 1 simultaneously, installs in the electric heating element 2 of the baffle lower surface of cavity 11, articulates and is located through first articulated elements 131 and the upper end of installing the first support column 13 on the bottom surface in the box 1 the flitch 30 of putting of electric heating element 2 lower extreme, the both ends that put flitch 30 and be located feed inlet and discharge gate department install first baffle 32 and second baffle 33 respectively and be used for thermal-insulated, and in order to avoid influencing the feeding, first baffle 32 highly lower, and with what the one side underrun of flitch 30 was connected through connecting piece 15 is fixed in cylinder 14 on the bottom surface in the box 1. The upper surface of the material placing plate 30 is provided with a movable plate 31 for placing copper foil, the lower surface of the material placing plate 30 is bonded with a heat insulation layer 35 for heat insulation, and in order to avoid the heat insulation layer 35 from influencing the movement of the first support column 13 and the connecting piece 15, the heat insulation layer 35 is respectively provided with a first round hole 351 and a second round hole 352 which correspond to each other; sealing strips 36 are bonded to the two side ends of the material placing plate 30, which are different from the material inlet and the material outlet, and the arrangement of the heat insulation layer and the sealing strips 36 can prevent the high temperature from influencing the working environment at the lower part of the box body 1 to the maximum extent.
In this embodiment, when the cylinder is not in operation, the material placing plate 30 is in a horizontal position due to the friction between the sealing strips 36 at the two ends and the inner wall of the box 1, when the cylinder 14 pushes the material placing plate 30 upwards to lift the end close to the discharge port, the end of the material placing plate 30 located at the feed port sinks, when the inclination angle is stable, the copper foil can be placed on the movable plate 31 outside, then the whole movable plate 31 is placed on the material placing plate 30 from the feed port, then the cylinder 14 pulls the end of the material placing plate 30 close to the discharge port to descend until the material placing plate 30 returns to the horizontal state to perform material drying, after the material drying is completed, the cylinder 14 further pulls the end of the material placing plate 30 close to the discharge port to descend, when the inclination angle is stable, the whole movable plate 31 can be moved out from the discharge port, and finally, the cylinder pushes the material placing plate 30 to return to the horizontal state again, thereby completing one cycle.
In this embodiment, the connecting member 15 includes a first connecting member 152 connected to the pushing rod 141 of the cylinder 14 and having a first groove 152a, a second connecting member 153 disposed in the first groove 152a and screwed to the groove walls of the first groove 152a and having a second groove 153a for allowing the pushing rod 141 to pass through, and a second hinge member 151 connected to the upper end of the second connecting member 153 and connected to the lower surface of the material placing plate 30.
In this embodiment, the lower surface of the first connecting member 152 is further provided with a first channel 152b communicated with the first groove 152a and allowing the push rod 141 to pass through, the push rod 141 is respectively sleeved with a first limit ring 141a located at the lower end of the first channel 152b and a second limit ring 141b located at the upper end of the first channel 152b, the lower end of the second limit ring 141b is further bonded with a gasket 141c, the first limit ring 141a is arranged to push the whole connecting member 15 to move upwards, the second limit ring 141b is arranged to pull the whole connecting member 15 to move downwards, the push rod 141 is prevented from falling off from the first groove 152a, and the gasket 141c prevents the second limit ring 141b from colliding with the first groove 152 a.
In this embodiment, the second limiting ring 141b is provided with a connecting rope 16, one end of which is fixed to the lower surface of the second limiting ring 141b through a limiting ball 161, and the other end of which sequentially passes through a mounting channel 141d formed in the second limiting ring 141b, a second channel 153b formed in the side wall of the second connecting member 153 and communicated with the second groove 153a, a third channel 301a formed in the material placing plate 30, and a second baffle 33 connected with a torsion spring 34 arranged on the inner bottom surface of the mounting groove 301 formed in the end of the material placing plate 30. In this embodiment, a first stopper 35 provided to the second barrier 33 is installed on a groove sidewall of the installation groove 301. And a second limiting rod 17 arranged at the lower end of the connecting rope 16 is arranged on the inner side wall of the box body 1.
In the present embodiment, the connecting rope 16 is designed to change the state of the second flap 33 when the cylinder 14 is operated: when the material placing plate 30 is horizontal, the connecting rope 16 is in a balanced state, the torsion spring piece 34 and the first limiting rod 35 act together to enable the included angle between the second baffle 33 and the surface of the material placing plate 30 to be an obtuse angle close to 90 degrees; when the cylinder 14 pushes the connecting piece 15 to ascend, the connecting rope 16 is in a tensioned state because the elongation is smaller than the displacement of the second baffle 33, at this time, the first limiting rod 35 is not connected with the second baffle 33, and the force generated by the torsion spring 34 is smaller than the pulling force of the connecting rope 16, so that the included angle between the second baffle 33 and the surface of the material placing plate 30 is an obtuse angle which is gradually increased until the stable state is reached, and therefore, the upper end of the baffle 33 cannot collide with the lower surface of the cavity 11 because one end of the material placing plate 30 is lifted; when the cylinder pulls the connecting piece 15 to sink, the connecting rope 16 becomes loose, but due to the existence of the second limiting rod 17, the connecting rope 16 becomes tight again, so that the second baffle 33 is pulled to enable the included angle between the second baffle 33 and the surface of the material placing plate 30 to gradually become larger and close to 180 degrees, at the moment, the second baffle 33 does not only not influence the blanking, but also is beneficial to further keeping the operating point of a worker away from a heat source.
Example 2
The embodiment provides a graphite material with long cycle characteristic for a lithium battery, which comprises the following components in parts by weight: 100 parts of graphite host material, 50 parts of carbonized material (obtained by carbonizing pitch coke and needle coke 1.
The preparation method of the carbonized material in the embodiment includes: the needle coke and the asphalt coke are crushed, shaped and mixed according to a certain proportion, and then are put into a carbonization furnace under the protection of inert gas and under the protection of a magnetic field of 440 ℃ for heat preservation reaction for 10 hours to obtain the carbonized material.
The preparation method of the graphite material in the embodiment is as follows: (1) Stirring the carbonized material in a shearing mixer at the intensity of 15Hz to obtain a mixed powder material; (2) Adding all CMC aqueous solution into the mixed powder material, and adjusting the frequency to be 25Hz to obtain a mixture; (3) Adding a natural graphite material into the obtained mixture, and adjusting the frequency to be 15Hz to obtain a coarse material; (4) Adding a surfactant and water into the obtained coarse material, adding all SBR aqueous solution, continuously stirring at a low frequency of 30Hz and a dispersion frequency of 30Hz, and uniformly mixing to obtain a graphite cathode material after the high-frequency stirring at a high frequency of 40Hz and the dispersion frequency of 50Hz until the viscosity reaches the standard; (5) And coating the obtained graphite negative electrode material on copper foil, and sending the copper foil into a drying oven for vacuum drying at 120 ℃ for 12 hours to prepare the graphite negative electrode sheet for the lithium battery.
This embodiment is the same as the drying oven used in embodiment 1, and therefore, the description thereof is omitted.
Example 3
The embodiment provides a graphite material with long cycle characteristic for a lithium battery, which comprises the following components in parts by weight: 100 parts of graphite host material, 25 parts of carbonized material (obtained by carbonizing pitch coke and needle coke 1.
The preparation method of the carbonized material in the embodiment comprises the following steps: crushing and shaping needle coke and pitch coke, mixing according to a certain proportion, and then carrying out heat preservation reaction for 12 hours in a carbonization furnace under the protection of inert gas and under the condition of applying a magnetic field of 420 ℃ to obtain the carbonized material.
The preparation method of the graphite material in the embodiment is as follows: (1) Stirring the carbonized material in a shearing mixer at the intensity of 15Hz to obtain a mixed powder material; (2) Adding all CMC aqueous solution into the mixed powder material, and adjusting the frequency to be 25Hz to obtain a mixture; (3) Adding a natural graphite material into the obtained mixture, and adjusting the frequency to be 15Hz to obtain a coarse material; (4) Adding a surfactant and water into the obtained coarse material, adding all SBR aqueous solution, continuously stirring and stirring at a low frequency of 25Hz and a dispersion frequency of 25Hz, and uniformly mixing to obtain a graphite cathode material after the high-frequency stirring and stirring frequency is 35Hz and the dispersion frequency is 45Hz until the viscosity reaches the standard; (5) And coating the obtained graphite negative electrode material on copper foil, and sending the copper foil into a drying oven for vacuum drying at 120 ℃ for 12 hours to prepare the graphite negative electrode sheet for the lithium battery.
This embodiment is the same as the drying oven used in embodiment 1, and therefore, the description thereof is omitted.
The graphite negative electrode sheets for lithium batteries obtained in the above examples 1 to 3 were assembled into batteries, and the batteries purchased in the market were set for comparative testing, and the performance of all the batteries was tested as follows:
as shown in the data in the table, the scheme adopted by the invention can greatly improve the cycle stability and the service life of the graphite cathode of the lithium ion secondary battery, and has higher capacity retention rate.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (9)
1. The graphite negative electrode material of the low-magnetism substance for the lithium battery is characterized by comprising the following components in parts by weight: 90 to 110 parts of graphite main body material, 10 to 50 parts of carbonization material, 5 to 10 parts of adhesive, 1 to 5 parts of surfactant and 1 to 500 parts of water, wherein the carbonization material is prepared from at least one of needle coke and asphalt coke through high-temperature reaction, heat preservation and magnetization; the preparation method of the carbonized material comprises the following steps: (1) Crushing needle coke and/or pitch coke and shaping to obtain crushed material; (2) And (3) putting the crushed material into a carbonization furnace under the conditions of inert gas protection and magnetic field, and carrying out heat preservation reaction at the temperature of 400-440 ℃ for 10-15h to obtain the carbonized material.
2. A method for preparing a graphite negative electrode material for a low magnetic substance for a lithium battery as claimed in claim 1, comprising the steps of:
the method comprises the following steps: placing the carbonized material in a shearing mixer with the vibration frequency of 10 to 15Hz for stirring to obtain a mixed powder material;
step two: adding 30-50% of adhesive in percentage by mass into the mixed powder material, and mixing at a vibration frequency of 15-25Hz to obtain a mixture;
step three: adding a graphite main body material into the mixture, and mixing at a frequency of 10-15Hz to obtain a coarse material;
step four: adding a surfactant and water into the coarse material, stirring at high frequency until the viscosity reaches the standard, adding the rest of the adhesive, and stirring at low frequency to mix uniformly to obtain graphite cathode slurry;
step five: and coating the graphite negative electrode slurry on a copper foil, and then sending the copper foil into a drying oven for drying to obtain the graphite negative electrode sheet for the lithium battery.
3. The preparation method of the graphite negative electrode material with low magnetic substance for the lithium battery as claimed in claim 2, wherein the stirring frequency of the high-frequency stirring is 30 to 40Hz, and the dispersion frequency is 40 to 50Hz; the stirring frequency of the low-frequency stirring is 20 to 30Hz, and the dispersion frequency is 20 to 30Hz.
4. The method for preparing a graphite cathode material with low magnetic substance for lithium battery as claimed in claim 2, wherein the drying oven in the fifth step comprises an oven body (1), an electric heating element (2) disposed in the oven body (1), a material placing plate (30) hinged to the upper end of the first support column (13) mounted on the inner bottom surface of the oven body (1) through a first hinge (131) and located at the lower end of the electric heating element (2), and a cylinder (14) fixed on the inner bottom surface of the oven body (1) and connected to the bottom surface of one side of the material placing plate (30) through a connector (15).
5. The method for preparing a graphite anode material of a low magnetic substance for a lithium battery as claimed in claim 4, wherein the connecting member (15) comprises a first connecting member (152) having a first groove (152 a) connected to the push rod (141) of the cylinder (14), a second connecting member (153) disposed in the first groove (152 a) and screwed to both side walls of the first groove (152 a) and having a second groove (153 a) for passing the push rod (141), and a second hinge member (151) connected to the upper end of the second connecting member (153) and connected to the lower surface of the material-placing plate (30).
6. The method for preparing the graphite anode material of the low-magnetic substance for the lithium battery as claimed in claim 5, wherein the lower surface of the first connecting member (152) is further provided with a first channel (152 b) which is communicated with the first groove (152 a) and enables the push rod (141) to pass through, and the push rod (141) is respectively sleeved with a first limit ring (141 a) positioned at the lower end of the first channel (152 b) and a second limit ring (141 b) positioned at the upper end of the first channel (152 b).
7. The method for preparing the graphite anode material with low magnetic substance for the lithium battery according to claim 6, wherein the second limiting ring (141 b) is provided with a second channel (153 b) which is connected with the second limiting ring (141 b) at one end and is communicated with the second groove (153 a) and is arranged on the side wall of the second connecting piece (153) and a connecting rope (16) which is connected with a second baffle (33) and penetrates through a third channel (301 a) arranged on the material placing plate (30) in sequence and is connected with a torsion spring piece (34) arranged on the inner bottom surface of a mounting groove (301) arranged on the end of the material placing plate (30).
8. The method for preparing a low-magnetic graphite anode material for a lithium battery as claimed in claim 7, wherein a first limiting rod (35) disposed on the second baffle (33) is mounted on a groove sidewall of the mounting groove (301).
9. The method for preparing the graphite anode material with low magnetic substance for the lithium battery as claimed in claim 7, wherein a second limiting rod (17) arranged at the lower end of the connecting rope (16) is installed on the inner side wall of the box body (1).
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