CN117673318A - Phenolic resin modified anode material, preparation method and application thereof, and lithium ion battery - Google Patents
Phenolic resin modified anode material, preparation method and application thereof, and lithium ion battery Download PDFInfo
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- CN117673318A CN117673318A CN202311796115.1A CN202311796115A CN117673318A CN 117673318 A CN117673318 A CN 117673318A CN 202311796115 A CN202311796115 A CN 202311796115A CN 117673318 A CN117673318 A CN 117673318A
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- 239000005011 phenolic resin Substances 0.000 title claims abstract description 107
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 107
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000010405 anode material Substances 0.000 title claims abstract description 69
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000005243 fluidization Methods 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 239000007921 spray Substances 0.000 claims description 40
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 39
- 239000007773 negative electrode material Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 13
- 239000003595 mist Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 16
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 15
- 239000002103 nanocoating Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 239000010426 asphalt Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002006 petroleum coke Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 for example Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a phenolic resin modified anode material, a preparation method and application thereof, and a lithium ion battery. The preparation method comprises the following steps: (1) Placing the anode material into a cavity of a fluidized bed reactor for fluidization; (2) Coating atomized phenolic resin on the surface of the fluidized anode material to obtain an anode material containing a coating layer; (3) Drying the anode material containing the coating layer to obtain a phenolic resin modified anode material; wherein, the mass ratio of the anode material to the phenolic resin is 100: (0.1-3). The phenolic resin modified anode material prepared by the invention has excellent stability and electrochemical performance when being used for preparing slurry, and the preparation method is simple, low in cost and beneficial to industrial production, and has the prospect of further popularization and application.
Description
Technical Field
The invention particularly relates to a phenolic resin modified anode material, a preparation method and application thereof, and a lithium ion battery.
Background
The surface of the existing common negative electrode materials such as silicon, hard carbon, natural graphite, artificial graphite and the like is almost free of hydrophilic groups, so that when the material is used as the negative electrode material of the lithium ion battery to prepare slurry, the processing problems of low processing stirring viscosity, sedimentation, abnormal coating appearance, low stripping efficiency and the like often occur; although the dispersing agent can uniformly disperse particles of the anode material to prevent aggregation and accumulation of the particles when the slurry is prepared, the whole energy density and charging performance of the battery cell can be affected when the dispersing agent is excessively added, so that the processing problem of the anode material cannot be completely solved by the dispersing agent.
Therefore, how to make the anode material have better stability when making slurry and excellent electrochemical performance when being applied to a battery under the condition of not adding a dispersing agent is a problem to be solved currently.
Disclosure of Invention
The invention solves the technical problems of poor stability, adverse processing and poor performance in lithium ion battery application of the lithium ion battery anode material in the prior art, and provides a phenolic resin modified anode material, a preparation method, application and a lithium ion battery. The phenolic resin modified anode material prepared by the invention has excellent stability and electrochemical performance when being used for preparing slurry, and the preparation method is simple, low in cost and beneficial to industrial production, and has the prospect of further popularization and application.
The invention solves the technical problems by the following technical proposal:
the invention provides a preparation method of a phenolic resin modified anode material, which comprises the following steps:
(1) Placing the anode material into a cavity of a fluidized bed reactor for fluidization;
(2) Coating atomized phenolic resin on the surface of the fluidized anode material to obtain an anode material containing a coating layer;
(3) Drying the anode material containing the coating layer to obtain the phenolic resin modified anode material;
wherein the mass ratio of the anode material to the phenolic resin is 100: (0.1-3).
In the present invention, the fluidization generally means that solid particles form a fluidization state under the drive of carrier gas. After the fluidization, the anode material is in a suspended state.
In the present invention, the mass ratio of the anode material to the phenolic resin is preferably 100: (0.2-2), for example 100:0.5, 100:1 or 100:1.5, more preferably 100: (0.7-2).
In step (1), the negative electrode material may be a lithium ion battery negative electrode material conventional in the art, typically a carbon-based negative electrode material or a silicon-based negative electrode material.
The silicon-based anode material can be a silicon oxygen material or a silicon carbon material.
Wherein the carbon-based negative electrode material may be one or more of artificial graphite, natural graphite, and hard carbon, for example, artificial graphite.
In step (1), when the negative electrode material is artificial graphite, the artificial graphite is commercially available, or is produced by a conventional method in the art, preferably the production method comprises the steps of: calcining and crushing petroleum coke and/or coal coke to obtain crushed material, and mixing, heat treating and graphitizing the mixture of the crushed material and asphalt to obtain artificial graphite.
Wherein, the petroleum coke is preferably the petroleum coke with S content less than or equal to 0.5 percent and ash content less than or equal to 0.1 percent. The coal char is preferably coal needle coke with S content less than or equal to 0.6% and ash content less than or equal to 0.1%.
Wherein the operation and conditions of the calcination may be conventional in the art. The calcination is generally carried out under an inert atmosphere, but may also be under a nitrogen atmosphere. Preferably, the inert atmosphere is a nitrogen and/or argon atmosphere.
The calcination temperature is preferably 800-1200 ℃, e.g. 1000 ℃. The calcination time is preferably 3 to 6 hours, for example 5 hours.
Wherein the operation and conditions of the comminution may be conventional in the art. Median particle diameter D of the crushed material 50 Preferably 6.0 to 12.0 μm; more preferably 6.0 to 10.0. Mu.m, for example 7.5. Mu.mm. When the median particle diameter of the pulverized material is more than 12.0 μm, the rate performance of the resulting artificial graphite may be degraded.
Among them, the asphalt is preferably an asphalt having a softening point of 150 to 280 ℃, for example, an asphalt having a softening point of 200 ℃.
Wherein the mass ratio of the pulverized material to the asphalt is preferably 100: (10-14), for example 100:12.
wherein the operation and conditions of the compounding may be conventional in the art, e.g. in a ribbon blender. The mixing time is preferably 30-90min, for example 60min.
Wherein the conditions and operation of the heat treatment may be conventional in the art, e.g. in a roller furnace. The heat treatment is typically carried out under an inert atmosphere, which may also be a nitrogen atmosphere. Preferably, the inert atmosphere is a nitrogen and/or argon atmosphere.
The temperature of the heat treatment is preferably 500-600 ℃, for example 550 ℃. The time of the heat treatment is preferably 3 to 8 hours, for example 6 hours.
Wherein the temperature of the graphitization treatment is preferably not less than 2600 ℃, more preferably not less than 2900 ℃, for example 2900 ℃. The graphitization treatment helps to stabilize the high energy density properties of the aggregate itself.
Wherein, after the graphitization treatment, the procedures of mixing, sieving and the like are preferably performed. The mixing and screening procedures can ensure the distribution uniformity of carbonized materials and the stability of powder materialization indexes.
The conditions and operation of the compounding may be conventional in the art. For example, the graphitized material may be mixed by a VC blender. The conditions and operation of the screening may be conventional in the art. For example, the blended material may be screened through an ultrasonic vibration screen XZS-800.
In the step (1), the particle diameter D of the anode material 50 May be 10-18 μm, for example 15.2 μm.
In step (1), the fluidized bed reactor cavity may be conventional in the art, such as a silo of a fluidized bed spray nano-coating reactor.
In step (1), the carrier gas used in the fluidization may be conventional in the art, such as nitrogen.
In the fluidization step (1), the flow rate of the carrier gas may be 5 to 20L/min, for example, 10L/min.
In step (2), the phenolic resin is preferably a water-soluble phenolic resin.
Wherein the free phenol content in the water-soluble phenolic resin may be < 2.5%. The free phenol content refers to the ratio of the mass of free phenol in the water-soluble phenolic resin to the mass of the water-soluble phenolic resin.
In step (2), the coating process preferably includes the steps of: and converting the phenolic resin into a nanoscale liquid phase mist in a spray generator of the fluidized bed reactor, and then spraying the liquid phase mist on the surface of the fluidized anode material.
The phenolic resin is typically introduced into the spray generator of the fluidized bed reactor in the form of a phenolic resin solution. In the phenolic resin solution, the solvent is typically deionized water. The phenolic resin solution may have a density of (0.06-0.03) g/cm 3 For example 0.01667g/cm 3 。
The flow rate of the phenolic resin into the spray generator may be (2-5) mL/min, for example 3mL/min.
The pressure at which the phenolic resin is sprayed from the spray generator may be (5-15) MPa, for example 10MPa.
The inlet temperature of the spray generator may be 170-180 ℃, for example 175 ℃.
The outlet temperature of the spray generator may be 150-160 ℃, for example 155 ℃.
When the inlet temperature and the outlet temperature of the spray generator are within the above-defined ranges, the fluidity and the spray state of the phenolic resin are better.
In step (3), the drying is preferably carried out in a fluidized bed reactor.
In step (3), the drying temperature may be 250-400 ℃, for example 300 ℃.
In step (3), the drying time may be 20 to 60 minutes, for example 30 minutes.
In step (3), the rate of heating to the temperature of the drying may be 2-10deg.C/min, for example 5deg.C/min.
In the invention, the drying temperature and the drying time can be determined according to the discharging state of the material, and the structure of the phenolic resin can be damaged when the temperature is too high or the time is too long; too low temperature or too short time can cause uncleanness of small molecular rows in the phenolic resin, and influence the processability of materials.
In the present invention, steps (1) to (3) are preferably all performed in the same apparatus, for example, all performed in a fluidized bed spray nano-coating reactor.
The invention also provides the phenolic resin modified anode material prepared by the preparation method of the phenolic resin modified anode material.
In the invention, the particle diameter D of the phenolic resin modified anode material 50 May be 10-18 μm, for example 15.0 μm, 15.2 μm or 15.3 μm.
In the invention, the tap density of the phenolic resin modified anode material can be 0.8-1.0g/cm 3 For example 0.85g/cm 3 、0.86g/cm 3 Or 0.87g/cm 3 。
In the present invention, the oxygen content of the phenolic resin modified anode material may be 0.03% -0.15%, for example 0.033%, 0.072% or 0.099%.
The invention also provides application of the phenolic resin modified anode material in a lithium ion battery.
The invention also provides a lithium ion battery, which comprises the phenolic resin modified anode material.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
the phenolic resin modified anode material prepared by the invention has excellent stability when being used for preparing slurry, has excellent electrochemical performance when being applied to a lithium ion battery, has excellent discharge capacity and first effect, also has better quick charge performance and rate capability, and has the advantages of simple preparation method, low cost, contribution to industrial production and further popularization and application prospect.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The reagents and equipment information used in the following examples and comparative examples are shown in Table 1:
TABLE 1
The raw material water-soluble phenolic resins used in the following examples and comparative examples have a free phenol content of < 2.5%; the water-soluble phenolic resin is subjected to the following treatment before use: dissolving solid water-soluble phenolic resin powder in deionized water to obtain water-soluble phenolic resin solution with density of 0.01667g/cm 3 ；
The preparation method of the artificial graphite comprises the following steps: adding petroleum coke into a horizontal coating kettle, calcining (1000 ℃ for 5 hours) in a nitrogen atmosphere, and then crushing by adopting a roll mill 300 machine to obtain a crushed material with the average particle diameter D50 of 7.5 mu m; mixing the crushed materials and asphalt with the mass ratio of 100:12 in a spiral belt mixer for 60min, and then performing heat treatment (550 ℃ for 6 h) in a roller furnace under the nitrogen atmosphere to obtain a heat-treated raw material; adding the heat-treated raw material into a graphitizing crucible furnace for graphitizing treatment, electrifying and heating to 2900 ℃, enabling the power transmission time to be 72 hours, stopping power transmission, and keeping the temperature for 30 days; mixing the graphitized material (in a VC mixer) and screening (in an ultrasonic vibration screen XZS-800) to obtain artificial graphite secondary particles;
in the petroleum coke, the S content is less than or equal to 0.5 percent and the ash content is less than or equal to 0.15; the softening point of the bitumen was 200 ℃.
Example 1
(1) 1000g of artificial graphite is added into a bin of a fluidized bed spray nano coating reactor, nitrogen is used as carrier gas, and the carrier gas flow is controlled at 10L/min to fluidize the artificial graphite;
(2) Introducing 30mL of water-soluble phenolic resin solution into a spray generator in a fluidized bed spray nano coating reactor at a flow rate of 3mL/min, converting the water-soluble phenolic resin solution into mist at a pressure of 10MPa, spraying the mist, and uniformly coating the mist on the surface of artificial graphite; wherein the inlet temperature of the spray generator is controlled to be 175 ℃, and the outlet temperature of the spray generator is controlled to be 155 ℃;
the mass ratio of the artificial graphite to the water-soluble phenolic resin solid powder is 100:0.5;
(3) After phenolic resin is completely coated on the surface of artificial graphite, the temperature in a fluidized bed spray nano coating reactor bin is raised to 300 ℃ at a heating rate of 5 ℃/min for low-temperature drying treatment, and the heat preservation temperature is constant at 300+/-3 ℃ for 30min; and after the test is finished, naturally cooling, and discharging to obtain the phenolic resin modified anode material.
Example 2
(1) 1000g of artificial graphite is added into a bin of a fluidized bed spray nano coating reactor, nitrogen is used as carrier gas, and the carrier gas flow is controlled at 10L/min to fluidize the artificial graphite;
(2) Introducing 60mL of water-soluble phenolic resin solution into a spray generator in a fluidized bed spray nano coating reactor at a flow rate of 3mL/min, converting the solution into mist at a pressure of 10MPa, spraying the mist out, and uniformly coating the surface of the artificial graphite; wherein the inlet temperature of the spray generator is controlled to be 175 ℃, and the outlet temperature of the spray generator is controlled to be 155 ℃;
the mass ratio of the artificial graphite to the water-soluble phenolic resin solid powder is 100:1, a step of;
(3) After phenolic resin is completely coated on the surface of artificial graphite, the temperature in a fluidized bed spray nano coating reactor bin is raised to 300 ℃ at a heating rate of 5 ℃/min for low-temperature drying treatment, and the heat preservation temperature is constant at 300+/-3 ℃ for 30min; and after the test is finished, naturally cooling, and discharging to obtain the phenolic resin modified anode material.
Example 3
(1) 1000g of artificial graphite is added into a bin of a fluidized bed spray nano coating reactor, nitrogen is used as carrier gas, and the carrier gas flow is controlled at 10L/min to fluidize the artificial graphite;
(2) 90mL of water-soluble phenolic resin solution is introduced into a spray generator in a fluidized bed spray nano coating reactor at a flow rate of 3mL/min, converted into mist at a pressure of 10MPa, sprayed out and uniformly coated on the surface of artificial graphite; wherein the inlet temperature of the spray generator is controlled to be 175 ℃, and the outlet temperature of the spray generator is controlled to be 155 ℃;
the mass ratio of the artificial graphite to the water-soluble phenolic resin solid powder is 100:1.5;
(3) After phenolic resin is completely coated on the surface of artificial graphite, the temperature in a fluidized bed spray nano coating reactor bin is raised to 300 ℃ at a heating rate of 5 ℃/min for low-temperature drying treatment, and the heat preservation temperature is constant at 300+/-3 ℃ for 30min; and after the test is finished, naturally cooling, and discharging to obtain the phenolic resin modified anode material.
Comparative example 1
Artificial graphite.
Comparative example 2
(1) 1000g of artificial graphite is added into a bin of a fluidized bed spray nano coating reactor, nitrogen is used as carrier gas, and the carrier gas flow is controlled at 10L/min to fluidize the artificial graphite;
(2) 300mL of water-soluble phenolic resin solution is introduced into a spray generator of a fluidized bed spray nano coating reactor at a flow rate of 3mL/min, converted into mist at a pressure of 10MPa, sprayed out and uniformly coated on the surface of artificial graphite; wherein the inlet temperature of the spray generator is controlled to be 175 ℃, and the outlet temperature of the spray generator is controlled to be 155 ℃;
the mass ratio of the artificial graphite to the water-soluble phenolic resin solid powder is 100:5, a step of;
(3) After phenolic resin is completely coated on the surface of artificial graphite, the temperature in a fluidized bed spray nano coating reactor bin is raised to 300 ℃ at a heating rate of 5 ℃/min for low-temperature drying treatment, and the heat preservation temperature is constant at 300+/-3 ℃ for 30min; and after the test is finished, naturally cooling, and discharging to obtain the phenolic resin modified anode material.
Effect examples
(1) The phenolic resin modified negative electrode materials prepared in examples 1 to 3, comparative example 2 and artificial graphite of comparative example 1 were respectively subjected to particle size and tap density tests according to conventional methods in the art, and the results are shown in table 2.
(2) Oxygen content test
The phenolic resin-modified anode materials prepared in examples 1 to 3 and comparative example 2 and the artificial graphite of comparative example 1 were respectively tested for surface oxygen content by infrared absorption using an oxygen-nitrogen meter, and the test results are shown in table 2.
(3) Zeta potential
The dispersion stability of the sample in the aqueous phase was measured using a nanoparticle size and Zeta potential analyzer, and the test results are shown in table 2. In general, a higher absolute value of Zeta potential indicates a more stable dispersion of the sample.
Electrochemical Property (half cell)
The phenolic resin modified anode materials obtained in the above examples 1-3 and comparative example 2 and the artificial graphite of comparative example 1 were respectively prepared into anode sheets, and assembled into button cells for electrochemical performance test, which comprises the following specific steps:
(a) The mass ratio of the phenolic resin modified anode material or the artificial graphite obtained in the above examples 1-3 and comparative examples 1-2 to CMC, SP, SBR was 95.5:1.5:1.5:1.5, mixing, adding deionized water, stirring until uniform, and preparing slurry;
(b) The slurry is coated on copper foil, baked in a vacuum drying oven at 90 ℃ for 24 hours, then rolled by a pair of rollers, and finally made into pole pieces (pole piece slurry load) by a sheet punching machine8.25mg/cm 2 )；
(c) Assembling the pole piece into a button cell by taking metal lithium as a counter electrode, wherein the assembling process is carried out in a vacuum glove box filled with high-purity nitrogen;
(d) Electrochemical performance testing is carried out after assembly is completed:
the discharge capacity and first effect test conditions were: under normal temperature, 0.1C constant current charge and discharge is carried out, and the voltage range is 0-2.0V;
inflection point SOC test conditions: the constant volume is carried out at the rate of 0.1C in the test, the voltage range is 0-2.0V, the current of 2.2C is discharged to 0% SOC, and the lithium-ion analysis point data are obtained through a Dv/dQ-Q curve; lithium precipitation point data were obtained by discharging the lithium ion battery to 0% SOC at a current of 3.0C and passing through a Dv/dQ-Q curve. The test results are shown in Table 2.
TABLE 2
As can be seen from table 2, the surface oxygen content of the phenolic resin modified anode materials prepared in examples 1 to 3 of the present invention is 0.033% to 0.099%; the phenolic resin modified anode material has better stability after being prepared into slurry; when applied to lithium ion batteries, the lithium ion battery has better discharge capacity, first effect and quick charge performance.
As can be seen from table 2, the surface oxygen content of the artificial graphite anode material not modified with the phenolic resin in comparative example 1 was 0.021%; according to examples 1 to 3, it is understood that the surface oxygen content of the obtained phenolic resin modified anode material is increased after the phenolic resin modification is adopted, and the more hydroxyl groups on the surface of the phenolic resin modified anode material are likely to be hydrophilic as the addition amount of the phenolic resin is increased.
The phenolic resin modified anode material prepared by the invention can improve the stability of battery slurry. The Zeta potential value of the artificial graphite anode material which is not modified by the phenolic resin in the comparative example 1 is-19.7 mV, which indicates that the corresponding slurry is in an unstable state; the Zeta potential value of the phenolic resin modified anode material obtained in example 1 is-25.7 mV, which shows that the stable state of the corresponding slurry is improved and gradually tends to be stable; the Zeta potential values of the phenolic resin modified anode materials obtained in the examples 2-3 are-32.1 mV and-34.9 mV respectively, which shows that the corresponding slurries have reached a relatively stable state; the above shows that: in a certain range, as the addition amount of the phenolic resin increases, the state of the battery slurry corresponding to the phenolic resin modified anode material is more and more stable.
The phenolic resin modified anode material prepared by the invention has excellent quick charge performance. The lithium ion battery prepared from the artificial graphite of comparative example 1 had a lithium precipitation point of 36% at a current of 2.2C, indicating that the battery had metallic lithium precipitated when charged to 36% soc at a constant current of 2.2C. The lithium ion batteries prepared from the phenolic resin modified anode materials of examples 1-3 all have lithium precipitation points of more than 40% under the charging current of 2.2C; under the 3C charging current, the lithium precipitation points are above 28%; and as the addition amount of the phenolic resin increases, the quick charge performance of the phenolic resin modified anode material increases, and after the addition amount of the phenolic resin increases to a certain level, the quick charge performance of the phenolic resin modified anode material tends to be stable.
As can be seen from comparative example 2, when the mass ratio of the artificial graphite to the water-soluble phenolic resin exceeds 100: when the range is (0.1-3), the battery slurry stability becomes poor and the quick-charge property becomes poor.
Claims (10)
1. The preparation method of the phenolic resin modified anode material is characterized by comprising the following steps of:
(1) Placing the anode material into a cavity of a fluidized bed reactor for fluidization;
(2) Coating atomized phenolic resin on the surface of the fluidized anode material to obtain an anode material containing a coating layer;
(3) Drying the anode material containing the coating layer to obtain the phenolic resin modified anode material;
wherein the mass ratio of the anode material to the phenolic resin is 100: (0.1-3).
2. The method for producing a phenolic resin modified negative electrode material according to claim 1, wherein the mass ratio of the negative electrode material to the phenolic resin is 100: (0.2-2), preferably 100: (0.7-2).
3. The method for producing a phenolic resin modified anode material according to claim 1 or 2, wherein the production method satisfies one or more of the following conditions:
(1) The negative electrode material is a carbon-based negative electrode material or a silicon-based negative electrode material;
the silicon-based anode material is preferably a silicon oxygen material or a silicon carbon material;
the carbon-based negative electrode material is preferably one or more of artificial graphite, natural graphite, and hard carbon;
(2) Particle diameter D of the negative electrode material 50 Preferably 10-18 μm; and, a step of, in the first embodiment,
(3) The phenolic resin is water-soluble phenolic resin;
the free phenol content of the water-soluble phenolic resin is preferably < 2.5%.
4. The method for producing a phenolic resin modified anode material according to claim 1 or 2, wherein the carrier gas used in the fluidization is nitrogen;
and/or, in the fluidization process, the flow rate of the carrier gas is 5-20L/min.
5. The method for producing a phenolic resin modified negative electrode material according to claim 1 or 2, wherein in the step (2), the coating process comprises the steps of: and converting the phenolic resin into a nanoscale liquid phase mist in a spray generator of the fluidized bed reactor, and then spraying the liquid phase mist on the surface of the fluidized anode material.
6. The method for preparing a phenolic resin modified negative electrode material of claim 5 wherein the coating satisfies one or more of the following conditions:
(1) The flow rate of the phenolic resin into the spray generator is (2-5) mL/min;
(2) The pressure of the phenolic resin when sprayed out from the spray generator is (5-15) MPa;
(3) The inlet temperature of the spray generator is 170-180 ℃;
(4) The outlet temperature of the spray generator is 150-160 ℃; and, a step of, in the first embodiment,
(5) The phenolic resin is introduced into a spray generator of the fluidized bed reactor in the form of phenolic resin solution; in the phenolic resin solution, the solvent is preferably deionized water; the density of the phenolic resin solution is preferably (0.06-0.03) g/cm 3 For example 0.01667g/cm 3 。
7. The method for producing a phenolic resin modified negative electrode material according to claim 1 or 2, wherein the drying temperature is 250 to 400 ℃;
and/or, the drying time is 20-60min.
8. A phenolic resin modified negative electrode material, characterized in that it is prepared by the preparation method of the phenolic resin modified negative electrode material according to any one of claims 1 to 7.
9. Use of the phenolic resin modified negative electrode material of claim 8 in lithium ion batteries.
10. A lithium ion battery comprising the phenolic resin modified negative electrode material of claim 8.
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