CN114695851B - Composite anode material, anode, battery and preparation method thereof - Google Patents
Composite anode material, anode, battery and preparation method thereof Download PDFInfo
- Publication number
- CN114695851B CN114695851B CN202011645714.XA CN202011645714A CN114695851B CN 114695851 B CN114695851 B CN 114695851B CN 202011645714 A CN202011645714 A CN 202011645714A CN 114695851 B CN114695851 B CN 114695851B
- Authority
- CN
- China
- Prior art keywords
- shell
- composite anode
- anode material
- composite
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000010405 anode material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 19
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 239000007773 negative electrode material Substances 0.000 claims abstract description 7
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims abstract description 4
- 235000011613 Pinus brutia Nutrition 0.000 claims abstract description 4
- 241000018646 Pinus brutia Species 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- 238000010000 carbonizing Methods 0.000 claims description 19
- 239000011302 mesophase pitch Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007770 graphite material Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 34
- 238000001035 drying Methods 0.000 description 24
- 238000007873 sieving Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013022 venting Methods 0.000 description 6
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
-
- 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
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
Abstract
The invention relates to the technical field of batteries, in particular to a composite anode material, an anode, a battery and a preparation method thereof. The composite anode material comprises soft carbon, and is of a waxberry-shaped or pine cone-shaped core-shell structure; wherein the shell is soft carbon. The shell of the composite anode material with the waxberry-shaped or pine-cone-shaped core-shell structure is porous soft carbon; the composite negative electrode material with the structure can simultaneously have the quick charge and quick discharge performance and the long-acting performance of life retention, and simultaneously overcomes the defects of insufficient capacity and low primary charging efficiency.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a composite anode material, an anode, a battery and a preparation method thereof.
Background
In recent years, as a novel energy storage battery, a lithium ion battery has made great progress in development and application; meanwhile, a fast-charging lithium ion battery has become an important development direction. Quick-charging lithium batteries have great demands in the field of mobile equipment, such as electric tools, electric automobiles, start-stop devices and the like. Because the fast charge lithium ion battery can realize fast charge and discharge, the development of the fast charge and fast discharge lithium ion electrode material has wide commercial prospect.
At present, most of the lithium ion anode materials used for quick charge are soft carbon materials, and the materials have low capacity and insufficient initial charging efficiency although the materials have quick charge performance.
Disclosure of Invention
The first object of the invention is to provide a composite anode material, which comprises soft carbon, wherein the composite anode material is in a waxberry-shaped or pine cone-shaped core-shell structure; wherein the shell is soft carbon.
The core of the invention can be a cathode material with high capacity, and the composite cathode material (shown in the figure 3 of the invention) with a waxberry-shaped or pine-cone-shaped core-shell structure is formed after soft carbon is coated, so that the composite cathode material has both quick charge and quick release performance and long-acting performance of life retention; meanwhile, the defects of insufficient capacity and low primary charging efficiency are overcome.
As one embodiment, the specific surface area of the composite anode material is 4.0-20.0m 2 /g; or 4.0-12.0m 2 /g; or 5.5-8.0m 2 And/g. The composite anode material of the invention is a material with large surface area, such as carbon nano tube, which is not added with conductive agent, and is usually 4.0-12.0m 2 /g; after adding carbon nanotube and other large surface area materials as conductive agent, the specific surface area is increased obviously, and example 13 reaches 20.0m 2 And/g. In addition, the gram capacity of the composite negative electrode material is obviously higher than that of the single soft carbon material, and can reach 320-380mAh/g.
As one embodiment, the D50 particle size of the composite anode material is in the range of 5-15 microns; or alternatively, 8-12 microns.
As one embodiment, the shell has a thickness of 2-3 microns; and/or the average particle size of the core is 3-12 microns; or alternatively, from 6 to 10 microns.
As one embodiment, the shell has a porosity of greater than 20%; alternatively, greater than 30%.
As an embodiment, the mass percentage of the shell layer is 5% -50% based on 100% of the total mass of the composite anode material; alternatively, 15% -30%.
As an embodiment, the core is made of at least one material selected from the group consisting of silicon, graphite, and silicon-carbon composite materials. Or alternatively, graphite. The graphite coated by the soft carbon increases the specific surface area of the anode material, is beneficial to reducing the resistance of lithium ion intercalation, reduces the diffusion migration resistance and the charge transfer resistance, improves the diffusion rate of lithium ions, and is beneficial to improving the rate capability of the lithium ion battery.
As one embodiment, the D50 particle size of the material of the core is in the range of 5-15 microns; or alternatively, from 6 to 10 microns.
As an embodiment, the raw material of the shell is selected from mesophase pitch.
As one embodiment, the D50 particle size of the raw material of the shell ranges from 5 to 15 microns; or alternatively, 8-12 microns.
The second object of the invention is to provide a negative electrode, which adopts the composite negative electrode material.
A third object of the present invention is to provide a battery employing the above-described negative electrode.
The fourth object of the present invention is to provide a method for preparing the above composite anode material, comprising the steps of: 1) Mixing the solvent and the raw materials to form a mixture; the raw materials include a raw material of a shell and a raw material of a core; the solvent can make the raw materials of the shell slightly soluble; 2) Carbonizing the mixture in inert atmosphere to obtain the composite anode material.
The invention selects a solvent which can make the shell raw material slightly soluble, namely only part of shell raw material is dissolved, and a thin layer liquid phase is formed on the surface of undissolved shell raw material. The invention adopts a solvent which can slightly dissolve the raw material of the shell, and after the slightly dissolved raw material of the shell is mixed with nuclear raw materials such as natural graphite, precursors of a large amount of raw materials of the shell can be formed on the outer layer of each graphite particle, and then the precursors are converted into porous carbon through carbonization, so that the waxberry-shaped or pine-cone-shaped core-shell structure can be formed.
As an embodiment, the raw material of step 1) further comprises a conductive agent; alternatively, the conductive agent is carbon nanotubes and/or carbon nanofibers (such as VGCF).
The method of forming the mixture of the present invention is not limited, and as an embodiment, the method of forming the mixture of step 1) includes: the shell raw material is first slightly dissolved by using a solvent, and then the core raw material is added to be mixed to form a mixture. As another embodiment, the method of forming a mixture of step 1) includes: the raw materials are mixed first, and then a solvent is added to mix, so as to form a mixture.
If the raw materials also contain a conductive agent, the addition mode is not limited. As an embodiment, the method of forming the mixture of step 1) includes: the shell raw material is slightly dissolved by using a solvent, and then the core raw material and the conductive agent are added to be mixed to form a mixture. As another embodiment, the method of forming a mixture of step 1) includes: the raw materials are mixed first, and then a solvent is added to mix, so as to form a mixture. As another embodiment, the method of forming a mixture of step 1) includes: mixing the shell raw material and the conductive agent, adding a solvent to slightly dissolve the shell raw material, and then adding the core raw material to mix to form a mixture.
As an embodiment, step 1) the mass ratio of the raw material of the shell to the raw material of the core is 0.1 to 3.0; alternatively, 0.2 to 0.5.
As an embodiment, the mass ratio of the solvent to the raw material of step 1) is 0.5 to 3.0.
As an embodiment, the mass ratio of the conductive agent in the raw material in step 1) is 0.1% -2.0%; or 0.1% -1.0%; alternatively, 0.5% to 1.0%.
In one embodiment, step 1) the solvent that renders the raw material of the shell slightly soluble is selected from at least one of alcohols, ketones, ethers and esters. Or the solvent is at least one selected from ethanol, ethyl acetate and n-methyl pyrrolidone.
As an embodiment, step 1) the slightly dissolving means that the mass of the raw material of the shell dissolved by the solvent accounts for 10% to 50% of the total mass of the raw material of the shell; alternatively, 20% -30%.
As an embodiment, the mixing of step 1) is a stirred mixing. The sparingly soluble feedstock particles may "flow" into proximity with most of the nuclear feedstock (e.g., graphite) during agitation and remain or adhere to the surface of the nuclear feedstock. The stirring and mixing speed of the step 1) is 600-1500 rpm; alternatively, 800-1000 revolutions per minute; the stirring and mixing time is 2-8 hours; alternatively, 2-6 hours; alternatively, 4-6 hours.
As an embodiment, step 2) the inert atmosphere is introduced in the carbonization treatment; or the inert atmosphere is introduced before and during the carbonization treatment.
In one embodiment, the inert atmosphere in step 2) is at least one of nitrogen, helium and argon.
As an embodiment, the temperature of the carbonization treatment in step 2) is 1000-1500 ℃; or 1100-1250 ℃.
As an embodiment, the carbonization treatment of step 2) takes 2 to 8 hours; or from 6 to 8 hours.
As an embodiment, the carbonization treatment of step 2) is a multi-stage gradient heating treatment. Step 2), the carbonization treatment is three-stage gradient heating treatment; the first stage gradient heating treatment is carried out, the temperature is raised to 100 ℃ to 300 ℃ and the temperature stays for 30 to 90 minutes, so as to remove small molecular organic components; the second stage gradient heating treatment is carried out, the temperature is raised from 100 ℃ to 300 ℃ to 600 ℃ to 900 ℃ and the temperature stays for 30 to 90 minutes, so as to remove organic components with larger molecules; and in the third stage, the gradient heating treatment is carried out, the temperature is increased from 600-900 ℃ to 1000-1200 ℃ and kept for 2-8 hours, the O, N and other elements in the shell raw material are removed, and the carbon in the shell raw material forms a partially ordered product and is tightly bonded with the surface of the core.
As an embodiment, step 2) further comprises drying the mixture before the carbonization treatment; the temperature of the drying treatment is 80-300 ℃. The drying treatment time is 1-3 hours. This step may remove the solvent from the residual raw material.
The composite anode material is prepared; if the powdery composite anode material is needed, the block-shaped composite anode material can be crushed and sieved, for example, the block-shaped composite anode material is put into a crusher, and after crushing, the powder-shaped composite anode material is obtained by sieving with a 200-300 mesh screen according to the requirement.
The shell of the composite anode material with the waxberry-shaped or pine-cone-shaped core-shell structure is porous soft carbon; the composite negative electrode material with the structure can simultaneously have the quick charge and quick discharge performance and the long-acting performance of life retention, and simultaneously overcomes the defects of insufficient capacity and low primary charging efficiency.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the application and together with the description, serve to explain the principles of the application. In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a SEM image of the surface of soft carbon prepared according to a comparative example of the present invention.
Fig. 2 is a surface SEM image of the composite anode material prepared in example 1 of the present invention.
Fig. 3 is an SEM image of the composite anode material prepared in example 1 of the present invention.
Fig. 4 is a magnification test chart of the buckling power prepared by the composite anode material of the embodiment 1.
Fig. 5 is a cycle test chart of the soft pack battery prepared from the composite anode material of example 1 of the present invention.
Detailed Description
In the following description, reference is made to the accompanying drawings, which describe several embodiments of the present application. It is to be understood that other embodiments may be utilized and that mechanical, structural and operational changes may be made without departing from the spirit and scope of the present invention. The following detailed description is not to be taken in a limiting sense, and the scope of various embodiments of the present invention is defined only by the claims of the issued patent. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Example 1
Preparing a mixture: 80 grams of graphite material and 24 grams of mesophase pitch material are mixed and then 150 grams of n-methylpyrrolidone (NMP) solvent is weighed into it. Stirring was carried out at a stirring rate of 1000 rpm for 4 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: drying at 200deg.C for 2 hr (air can be introduced), cooling, and taking out the sample, wherein the sample has no fluidity.
Carbonizing: the dried mixture was placed in a tube furnace, and nitrogen (N) was introduced at a flow rate of 100mL/min 2 ) Venting for 3-5min to remove air in the tube, regulating the gas flow to 50mL/min for continuous venting, and heating the tube furnace from room temperature to 300 ℃ for 30 min; then heating from 300 ℃ to 800 ℃ and staying for 30 minutes; finally, the temperature is increased from 800 ℃ to 1200 ℃, the heat is preserved for 3 hours, and the composite anode material is obtained after the furnace is naturally cooled.
Crushing and sieving: and (3) putting the blocky composite anode material into a pulverizer, pulverizing, and sieving with a 200-mesh screen to obtain the powdery composite anode material.
Example 2
Preparing a mixture: 80 grams of graphite material and 24 grams of mesophase pitch material were mixed and then 150 grams of ethanol solvent was weighed into it. Stirring was carried out at a stirring rate of 1000 rpm for 4 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: after drying at 80℃for 2 hours, the sample was taken after cooling, at which point the sample had no flow.
Carbonizing: as in example 1.
Crushing and sieving: same as in example 1
Example 3
Preparing a mixture: 60 g of graphite material and 35 g of mesophase pitch material were mixed, and 150 g of n-methylpyrrolidone (NMP) solvent was weighed into this and stirred for 4 hours at a stirring rate of 1000 rpm. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 4
Preparing a mixture: 60 grams of graphite material and 35 grams of mesophase pitch material were mixed and then 150 grams of ethanol solvent was weighed into it. Stirring was carried out at a stirring rate of 1000 rpm for 4 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 5
Preparing a mixture: 50 g of graphite material and 59 g of mesophase pitch material were mixed, and 150 g of n-methylpyrrolidone (NMP) solvent was then weighed into the mixture and stirred at a stirring rate of 1000 rpm for 4 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 6
Preparing a mixture: 50 grams of graphite material and 59 grams of mesophase pitch material were mixed and then 150 grams of ethanol solvent was weighed into it. Stirring was carried out at a stirring rate of 1000 rpm for 4 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 7
Preparing a mixture: 30 grams of graphite material and 82 grams of mesophase pitch material were mixed and then 150 grams of n-methylpyrrolidone (NMP) solvent was weighed into this using the stirring mixing regime of example 2.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 8
Preparing a mixture: 30 g of graphite material and 82 g of mesophase pitch material were mixed, and 150 g of ethanol solvent was weighed into it. The stirring and mixing mode of example 3 was used.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 9
Preparing a mixture: as in example 1.
And (3) drying: as in example 1.
Carbonizing: the dried mixture was placed in a tube furnace, and nitrogen (N) was introduced at a flow rate of 100mL/min 2 ) Venting for 3-5min to remove air in the tube, regulating the gas flow to 50mL/min for continuous venting, setting sintering temperature and time, and keeping the tube furnace from room temperature to 300 ℃ for 30 min and then rising to 800 ℃ for 30 min; finally, the temperature is increased from 800 ℃ to 1000 ℃ (gradient temperature increasing mode), the heat is preserved for 8 hours, and the composite anode material is obtained after the furnace is naturally cooled.
Crushing and sieving: as in example 1.
Example 10
Preparing a mixture: as in example 1.
And (3) drying: as in example 1.
Carbonizing: the dried mixture was placed in a tube furnace, and nitrogen (N) was introduced at a flow rate of 100mL/min 2 ) Venting for 3-5min to remove air in the tube, regulating the gas flow to 50mL/min for continuous venting, setting sintering temperature and time, and keeping the tube furnace from room temperature to 300 ℃ for 30 min and then rising to 800 ℃ for 30 min; finally, the temperature is increased from 800 ℃ to 1500 ℃, the heat is preserved for 2 hours, and the composite anode material is obtained after the furnace is naturally cooled.
Crushing and sieving: as in example 1.
Example 11
Preparing a mixture: 80 grams of graphite material and 24 grams of mesophase pitch material were mixed, 1 gram of vgcf was weighed into it, and 150 grams of n-methylpyrrolidone (NMP) was weighed into it. The stirring and mixing mode was used in example 2.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 12
Preparing a mixture: 80 grams of graphite material and 24 grams of mesophase pitch material were mixed, 0.5 grams of VGCF was weighed into it, and 150 grams of n-methylpyrrolidone (NMP) was weighed into it. Stirring was carried out at a stirring rate of 1000 rpm for 4 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 13
Preparing a mixture: 80 grams of graphite material and 24 grams of mesophase pitch material were mixed and 12.5 grams (5% cnt carbon tube/NMP) of the slurry was weighed into it, followed by 150 grams of n-methylpyrrolidone (NMP) being weighed into it. Stirring was carried out at a stirring rate of 1000 rpm for 4 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 14
Preparing a mixture: 80 grams of graphite material and 24 grams of mesophase pitch material are mixed and then 150 grams of n-methylpyrrolidone (NMP) solvent is weighed into it. Stirring was carried out at a stirring rate of 600 rpm for 6 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 15
Preparing a mixture: 80 grams of graphite material and 24 grams of mesophase pitch material are mixed and then 150 grams of n-methylpyrrolidone (NMP) solvent is weighed into it. Stirring was carried out at a stirring rate of 1500 rpm for 2 hours. After stopping stirring, a mixture with a certain fluidity was formed.
And (3) drying: as in example 1.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 16
Preparing a mixture: as in example 1.
And (3) drying: the sample was dried at 150℃for 3 hours (air was allowed to pass through), and after cooling, the sample was taken out, at which point the sample had no fluidity.
Carbonizing: as in example 1.
Crushing and sieving: as in example 1.
Example 17
Preparing a mixture: as in example 1.
And (3) drying: the sample was dried at 300℃for 1 hour (air was allowed to pass through), cooled and taken out, at which point the sample had no fluidity.
Carbonizing: as in example 2.
Crushing and sieving: as in example 1.
Comparative example 1
Taking 100g of mesophase pitch raw material, putting the mesophase pitch raw material into a crucible, feeding the crucible into a tubular furnace, then introducing nitrogen at a flow rate of 100mL/min, ventilating for 3-5min to remove air in the tube, regulating the gas flow rate to 50mL/min for continuous ventilation (ventilation mode), heating the tubular furnace to 1200 ℃, sintering for 6 hours, naturally cooling, and taking out a sample to obtain 83g of soft carbon material.
Crushing and sieving: and (3) putting the soft carbon material into a pulverizer, pulverizing, and sieving with a 200-mesh screen to obtain soft carbon material powder.
Characterization of physical Properties of materials
The materials of all the above examples and comparative examples were subjected to physical property analysis, and the particle size distribution D50 (particle size analysis tester) and specific surface area of the test material powders were shown in tables 1 and 2. Wherein, the SEM of the surface morphology of comparative example 1 is shown in FIG. 1, and the SEM of the surface morphology of example 1 is shown in FIG. 2.
The specific surface area testing method comprises the following steps: the materials prepared in the above examples and comparative examples were baked at 150℃for 2 hours and then tested using the fine micro-high-Bobo BK300, the apparatus using a dynamic nitrogen adsorption method.
Particle size fraction testing: performed using a particle size analyzer-malvern 3000E.
TABLE 1
TABLE 2
Electrochemical performance test
1. Button cells were prepared and button cell tests were performed with soft carbon (prepared in comparative example 1), graphite (SG-8, a trade company of honest , su zhou limited), and a composite anode material (prepared in example 1) as an anode active material, respectively. The preparation method of the buckling electricity comprises the following steps: soft carbon or graphite or the powder of the embodiment 1, conductive carbon black and polyvinylidene fluoride (PVDF) are respectively and uniformly mixed according to the mass ratio of 90:5:5, and a proper amount of n-methyl pyrrolidone (NMP) is added, and after uniform stirring, the mixture is coated on copper foil. And (3) drying after coating, rolling on a roll squeezer, and cutting into the pole piece required by the button cell. And finally, putting the pole piece into a vacuum drying oven for drying. And assembling the battery in a glove box, wherein the manufactured pole piece is used as a negative electrode, and the metal lithium piece is used as a counter electrode. Electrolyte solvent composition 1mol/L LiPF 6 Ethylene Carbonate (EC) -diethyl carbonate (DEC) (volume ratio 3:7). The button cell battery was tested in a new-wire battery tester (5V 10mA new-wire button test cabinet).
Test conditions: and testing constant current charge and discharge by using 0.1C current and 0.01-1.5V voltage. The test results are shown in Table 3.
2. The power was tested for the snap-on power prepared in example 1 above, test conditions: constant current charge and discharge are respectively carried out by 0.1C,0.5C,1C and 2C currents. The test results are shown in FIG. 4.
3. Small soft package battery test: and (3) respectively testing small soft package batteries of the cathode composite material, and proportioning positive electrodes: ternary NCM 523: conductive agent: pvdf=95:2:3. The proportion of the negative electrode: composite anode material prepared in example 1: conductive agent: pvdf=96:2:2. Electrolyte solvent composition DMC/EC/DEC=1:1:1 (volume ratio), 1mol/L LiPF 6 And (3) a lithium salt. And manufacturing a 5Ah small soft package battery, performing battery test on a Xinwei battery test cabinet (5V 60A Xinwei battery test cabinet), performing constant current charge-discharge cycle test under the test condition of 3C3D current and 2.7-4.25V voltage at normal temperature until the battery cycle capacity reaches 80% of the initial capacity. The test results are shown in FIG. 5.
TABLE 3 Table 3
| Negative electrode material | First charge mAh/g | First discharge mAh/g | First time efficiency |
| Soft carbon | 308.2 | 250.3 | 81.2 |
| Graphite | 427.5 | 360.9 | 84.4％ |
| CoatingRear part (S) | 383.5 | 336.7 | 87.8％ |
Claims (18)
1. The preparation method of the composite anode material comprises the following steps: 1) Mixing the solvent and the raw materials to form a mixture; the raw materials include a raw material of a shell and a raw material of a core; the mass ratio of the raw material of the shell to the raw material of the core is 0.1-3.0; the raw material of the shell is selected from mesophase pitch; the solvent can make the raw materials of the shell slightly soluble; the slightly soluble refers to that the mass of the raw material of the shell dissolved by the solvent accounts for 10% -50% of the total mass of the raw material of the shell; 2) Carbonizing the mixture in an inert atmosphere to obtain the composite anode material, wherein the composite anode material is of a waxberry-shaped or pine cone-shaped core-shell structure; the shell of the composite anode material is porous soft carbon.
2. A method of preparing as claimed in claim 1, wherein: the raw materials in the step 1) also comprise a conductive agent.
3. A method of preparation as claimed in claim 1 or 2, characterized in that: the mass ratio of the solvent to the raw materials in the step 1) is 0.5-3.0.
4. A method of preparation as claimed in claim 2, wherein: the mass ratio of the conductive agent in the raw materials in the step 1) is 0.1% -2.0%.
5. A method of preparing as claimed in claim 1, wherein: the solvent in the step 1) is at least one selected from alcohols, ketones, ethers and esters.
6. A method of preparing as claimed in claim 5, wherein: the solvent is at least one selected from ethanol, ethyl acetate and n-methyl pyrrolidone.
7. A method of preparing as claimed in claim 1, wherein: the temperature of the carbonization treatment in the step 2) is 1000-1500 ℃; the carbonization treatment time is 2-8 hours.
8. A method of preparing as claimed in claim 1, wherein: the carbonization treatment in the step 2) is a multi-stage gradient heating treatment.
9. A method of preparing as claimed in claim 8, wherein: step 2), the carbonization treatment is three-stage gradient heating treatment; the first stage gradient heating treatment is carried out, the temperature is raised to 100 ℃ to 300 ℃ and the temperature stays for 30 to 90 minutes; the second stage gradient heating treatment is carried out, the temperature is raised from 100 ℃ to 300 ℃ to 600 ℃ to 900 ℃ and the temperature stays for 30 to 90 minutes; and in the third stage, the gradient heating treatment is carried out, the temperature is increased from 600-900 ℃ to 1000-1200 ℃ and the temperature is kept for 2-8 hours.
10. A composite negative electrode material prepared by the preparation method according to any one of claims 1 to 9, characterized in that: the composite anode material is of a waxberry-shaped or pine cone-shaped core-shell structure; wherein the shell is porous soft carbon.
11. The composite anode material of claim 10, wherein: the specific surface area of the composite anode material is 4.0-20.0m 2 /g。
12. The composite anode material of claim 10, wherein: the D50 particle size range of the composite anode material is 5-15 microns.
13. The composite anode material of claim 10, wherein: the shell has a thickness of 2-3 microns; and/or the average particle size of the core is 3-12 microns.
14. The composite anode material of claim 10, wherein: the shell has a porosity of greater than 20%.
15. The composite anode material of claim 10, wherein: the mass percentage of the shell layer is 5-50% based on 100% of the total mass of the composite anode material.
16. The composite anode material of claim 10, wherein: the core is made of at least one material selected from silicon, graphite and silicon-carbon composite materials.
17. A negative electrode using the composite negative electrode material according to any one of claims 10 to 16.
18. A battery employing the anode of claim 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011645714.XA CN114695851B (en) | 2020-12-31 | 2020-12-31 | Composite anode material, anode, battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011645714.XA CN114695851B (en) | 2020-12-31 | 2020-12-31 | Composite anode material, anode, battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114695851A CN114695851A (en) | 2022-07-01 |
| CN114695851B true CN114695851B (en) | 2024-04-09 |
Family
ID=82135700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011645714.XA Active CN114695851B (en) | 2020-12-31 | 2020-12-31 | Composite anode material, anode, battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114695851B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114695851B (en) * | 2020-12-31 | 2024-04-09 | 湖州欧美化学有限公司 | Composite anode material, anode, battery and preparation method thereof |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2674783A1 (en) * | 2008-12-02 | 2010-06-02 | Kokam Co., Ltd. | Core-shell anode material comprising positive temperature co-effecient medium for lithium secondary battery |
| CN101969122A (en) * | 2010-09-14 | 2011-02-09 | 东莞市迈科新能源有限公司 | Core-shell structured carbon for cathode material of lithium ion battery and preparation method thereof |
| CN103000867A (en) * | 2012-12-13 | 2013-03-27 | 天津市贝特瑞新能源科技有限公司 | Composite graphite negative electrode material with high energy density, and preparation method and application thereof |
| CN103151497A (en) * | 2013-03-16 | 2013-06-12 | 无锡东恒新能源材料有限公司 | Preparation method of negative material for low-temperature lithium ion battery |
| KR20130107892A (en) * | 2012-03-23 | 2013-10-02 | 강원대학교산학협력단 | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN103500815A (en) * | 2013-09-26 | 2014-01-08 | 深圳市贝特瑞新能源材料股份有限公司 | Soft-carbon composite cathode material of lithium ion battery and preparation method thereof |
| JP2014130821A (en) * | 2012-12-28 | 2014-07-10 | Btr New Energy Materials Inc | Lithium ion battery soft carbon negative electrode material and method for producing the same |
| CN104393262A (en) * | 2014-10-22 | 2015-03-04 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon composite anode material and preparation method thereof, as well as lithium ion battery containing same |
| CN105591084A (en) * | 2016-03-11 | 2016-05-18 | 深圳市贝特瑞新能源材料股份有限公司 | Negative electrode active material and preparation method thereof |
| JP2016110969A (en) * | 2014-05-07 | 2016-06-20 | 東ソー株式会社 | Negative electrode active material for lithium ion secondary battery, and manufacturing method thereof |
| CN106252596A (en) * | 2016-08-05 | 2016-12-21 | 深圳市贝特瑞新能源材料股份有限公司 | Soft carbon graphite composite negative pole material, preparation method and lithium ion battery |
| CN106299277A (en) * | 2016-08-30 | 2017-01-04 | 浙江超威创元实业有限公司 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| CN107408698A (en) * | 2015-03-23 | 2017-11-28 | 株式会社Lg 化学 | Negative active core-shell material and its preparation method |
| CN111354937A (en) * | 2020-04-21 | 2020-06-30 | 隆能科技(南通)有限公司 | Preparation method of core-shell structure high-capacity silicon-carbon composite negative electrode material for lithium ion battery |
| WO2020228151A1 (en) * | 2019-05-16 | 2020-11-19 | 贝特瑞新材料集团股份有限公司 | Core-shell composite negative electrode material, preparation method therefor and application thereof |
| CN114695850A (en) * | 2020-12-31 | 2022-07-01 | 湖州欧美化学有限公司 | Composite negative electrode material, negative electrode, battery and preparation method thereof |
| CN114695851A (en) * | 2020-12-31 | 2022-07-01 | 湖州欧美化学有限公司 | Composite negative electrode material, negative electrode, battery and preparation method of composite negative electrode material |
-
2020
- 2020-12-31 CN CN202011645714.XA patent/CN114695851B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2674783A1 (en) * | 2008-12-02 | 2010-06-02 | Kokam Co., Ltd. | Core-shell anode material comprising positive temperature co-effecient medium for lithium secondary battery |
| CN101969122A (en) * | 2010-09-14 | 2011-02-09 | 东莞市迈科新能源有限公司 | Core-shell structured carbon for cathode material of lithium ion battery and preparation method thereof |
| KR20130107892A (en) * | 2012-03-23 | 2013-10-02 | 강원대학교산학협력단 | Negative active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN103000867A (en) * | 2012-12-13 | 2013-03-27 | 天津市贝特瑞新能源科技有限公司 | Composite graphite negative electrode material with high energy density, and preparation method and application thereof |
| JP2014130821A (en) * | 2012-12-28 | 2014-07-10 | Btr New Energy Materials Inc | Lithium ion battery soft carbon negative electrode material and method for producing the same |
| CN103151497A (en) * | 2013-03-16 | 2013-06-12 | 无锡东恒新能源材料有限公司 | Preparation method of negative material for low-temperature lithium ion battery |
| CN103500815A (en) * | 2013-09-26 | 2014-01-08 | 深圳市贝特瑞新能源材料股份有限公司 | Soft-carbon composite cathode material of lithium ion battery and preparation method thereof |
| JP2016110969A (en) * | 2014-05-07 | 2016-06-20 | 東ソー株式会社 | Negative electrode active material for lithium ion secondary battery, and manufacturing method thereof |
| CN104393262A (en) * | 2014-10-22 | 2015-03-04 | 深圳市贝特瑞新能源材料股份有限公司 | Carbon composite anode material and preparation method thereof, as well as lithium ion battery containing same |
| CN107408698A (en) * | 2015-03-23 | 2017-11-28 | 株式会社Lg 化学 | Negative active core-shell material and its preparation method |
| CN105591084A (en) * | 2016-03-11 | 2016-05-18 | 深圳市贝特瑞新能源材料股份有限公司 | Negative electrode active material and preparation method thereof |
| CN106252596A (en) * | 2016-08-05 | 2016-12-21 | 深圳市贝特瑞新能源材料股份有限公司 | Soft carbon graphite composite negative pole material, preparation method and lithium ion battery |
| CN106299277A (en) * | 2016-08-30 | 2017-01-04 | 浙江超威创元实业有限公司 | A kind of silicon-carbon composite cathode material of lithium ion battery and preparation method thereof |
| WO2020228151A1 (en) * | 2019-05-16 | 2020-11-19 | 贝特瑞新材料集团股份有限公司 | Core-shell composite negative electrode material, preparation method therefor and application thereof |
| CN111354937A (en) * | 2020-04-21 | 2020-06-30 | 隆能科技(南通)有限公司 | Preparation method of core-shell structure high-capacity silicon-carbon composite negative electrode material for lithium ion battery |
| CN114695850A (en) * | 2020-12-31 | 2022-07-01 | 湖州欧美化学有限公司 | Composite negative electrode material, negative electrode, battery and preparation method thereof |
| CN114695851A (en) * | 2020-12-31 | 2022-07-01 | 湖州欧美化学有限公司 | Composite negative electrode material, negative electrode, battery and preparation method of composite negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| "废石墨化学沉积包覆作锂离子蓄电池负极材料";张永刚等;《电源技术研究与设计》;第130卷(第12期);第960-966页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114695851A (en) | 2022-07-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201820688A (en) | Cathode slurry for lithium ion battery | |
| KR20220092556A (en) | Anode active material for battery and manufacturing method thereof, battery negative electrode, battery | |
| CN107026262B (en) | High-capacity spherical hard carbon negative electrode material coated with graphene on surface | |
| CN103904307A (en) | Silicon-carbon composite material, preparation method and application thereof | |
| CN111029578B (en) | Modified hard carbon negative electrode material and preparation method thereof | |
| CN102569788B (en) | Negative material of a kind of lithium ion battery and preparation method thereof and a kind of lithium ion battery | |
| CN105633365A (en) | Composite cathode material for lithium-ion battery and preparation method of composite cathode material | |
| CN112582617A (en) | Nitrogen-selenium co-doped porous carbon sphere and sodium ion battery cathode material, and preparation method and application thereof | |
| KR20160078720A (en) | Negative electrode active material for rechargeable lithium battery, method for manufacturing the same, and rechargeable lithium battery including the same | |
| CN109524629B (en) | Preparation method of spherical silicon-carbon negative electrode material for lithium ion battery | |
| CN113644252A (en) | Silicon-carbon negative electrode material and preparation method thereof | |
| CN113401897B (en) | Preparation method of black phosphorus-based graphite composite lithium ion battery negative electrode material | |
| CN107565099B (en) | Positive active material, preparation method thereof and lithium ion battery | |
| CN114695851B (en) | Composite anode material, anode, battery and preparation method thereof | |
| CN112736242A (en) | High-performance carbon negative electrode PTCDA hard carbon material and preparation method thereof | |
| CN105375012B (en) | Silicon-tin composite material for lithium ion battery cathode and preparation method thereof | |
| CN108878823B (en) | Preparation method of metal olivine coated nano silicon | |
| CN108565431B (en) | Method for preparing silicon-carbon composite negative electrode material of lithium ion battery by taking konjac flour as carbon source | |
| CN114497481B (en) | Conductive polymer coated nano silicon powder, preparation method and application thereof, and silicon-carbon negative electrode material | |
| CN114695850A (en) | Composite negative electrode material, negative electrode, battery and preparation method thereof | |
| CN107256966B (en) | Lithium ion battery positive pole piece and preparation method thereof | |
| TW201320450A (en) | Manufacturing method of using modified artificial graphite as cathode material of lithium battery | |
| CN112072084B (en) | Composite electrode material and preparation method and application thereof | |
| CN114583137B (en) | Method for modifying carbon surface by sulfur doped phosphorus and application thereof | |
| CN114388878B (en) | Composite solid electrolyte and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |