CN114975966B - Aluminum-carbon coated graphite negative electrode material for lithium ion battery and preparation method thereof - Google Patents
Aluminum-carbon coated graphite negative electrode material for lithium ion battery and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 83
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 54
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 41
- 239000010439 graphite Substances 0.000 title claims abstract description 41
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000011812 mixed powder Substances 0.000 claims abstract description 25
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 22
- 229920006389 polyphenyl polymer Polymers 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011331 needle coke Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 72
- 238000000227 grinding Methods 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 29
- 239000010405 anode material Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 26
- 238000009210 therapy by ultrasound Methods 0.000 claims description 26
- 238000003837 high-temperature calcination Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 12
- 229920001568 phenolic resin Polymers 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000010298 pulverizing process Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract description 5
- 239000011247 coating layer Substances 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000007770 graphite material Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 208000028659 discharge Diseases 0.000 description 28
- 238000001514 detection method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H—ELECTRICITY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
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Abstract
The invention discloses a novel aluminum-carbon coated graphite negative electrode material for a lithium ion battery and a preparation method thereof, and belongs to the technical field of modification of lithium ion batteries and graphite materials. The novel aluminum-carbon coated graphite negative electrode material for the lithium ion battery comprises carbon material powder composed of needle coke and natural graphite; aluminum-coated carbon powder; the mixed powder and polyphenyl and hexabenzol form an aluminum-carbon coating layer. The novel aluminum-carbon coated graphite negative electrode material prepared by the process method can effectively inhibit voltage hysteresis, improves use safety, has higher initial capacity and excellent cycle performance, and has a capacity retention rate of nearly 80% in 500 cycles under the use condition of lower temperature, thereby effectively overcoming the defects of the graphite negative electrode material prepared by the conventional process and having good market competitiveness.
Description
Technical Field
The invention belongs to the technical field of modification of lithium ion batteries and graphite materials, and particularly relates to an aluminum-carbon coated graphite negative electrode material for a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery is a battery in which a carbon material is used as a negative electrode, a metal oxide capable of absorbing and desorbing lithium ions is used as a positive electrode, and lithium ions are intercalated and deintercalated in charge and discharge. The existing lithium ion battery effectively overcomes the defect of safety performance of the traditional lithium battery caused by lithium dendrite, has the advantages of high energy density, high average output voltage, small self discharge, good cycle performance, long service life and the like, and is the battery which is most widely applied in products such as mobile phones, notebook computers, electric bicycles and the like at present.
The lithium ion battery is still a very large improvement space in performance as a high-energy battery, wherein the key point is the negative electrode material of the battery, so the negative electrode material of the lithium ion battery is always the core focus of research and development in recent years, and the negative electrode material mainly researched at present comprises carbon materials including graphitized carbon materials and amorphous carbon materials, and non-carbon materials including silicon-based materials, transition metal oxides, metal nitrides and other alloy negative electrode materials. The natural graphite has larger external surface area, and the natural graphite cathode can generate excessive passivation layers in the first charge and discharge process, thereby generating the defects of irreversible capacity loss and voltage hysteresis. In addition, although the research of the negative electrode material of the lithium ion battery has been well developed in the prior art, as patent No. 201310489004.6 discloses a modified negative electrode material of the lithium ion battery graphite crucible waste and a preparation method thereof, patent No. 20161198334. X discloses a negative electrode material of the lithium ion battery graphite and a preparation method thereof, the prepared lithium ion battery has obviously improved performances such as charging capacity, cycle performance, charging and discharging efficiency, rate capability and the like, and the practical application value of the lithium ion battery is greatly improved; however, in some lower temperature environments, the performance of the battery still cannot be kept at an original high level, so that the application of the lithium ion battery in a few fields still has obvious limitations.
In view of this, there is a need for a graphite negative electrode material for lithium ion batteries that has superior discharge performance in a lower temperature environment.
Disclosure of Invention
Aiming at the technical defects that the prior art is used for preparing the graphite negative electrode material of the lithium ion battery, the voltage hysteresis and the prior high-level discharge cycle performance cannot be maintained under the low-temperature condition are mentioned in the background art, the invention aims to provide the aluminum-carbon coated graphite negative electrode material for the lithium ion battery and the preparation method thereof, and aims to solve the use safety of the lithium ion battery and improve the discharge and cycle performance of the lithium ion battery in the low-temperature environment.
The invention is realized by the following technical scheme:
The invention provides an aluminum-carbon coated graphite anode material for a lithium ion battery, which comprises the following components:
carbon material powder composed of needle coke and natural graphite;
Aluminum-coated carbon powder;
The mixed powder and polyphenyl, hexabenzol and phenolic resin form an aluminum-carbon coating layer.
The invention also provides a preparation method of the aluminum-carbon coated graphite anode material for the lithium ion battery, which comprises the following steps:
1) Pulverizing needle coke, calcining at high temperature in a furnace, cooling, and grinding into coke powder;
2) Mixing the coke powder obtained in the step 1) with natural graphite powder, adding the mixture into concentrated sulfuric acid, carrying out ultrasonic treatment, drying, then transferring into a furnace, calcining at high temperature, cooling, and grinding to obtain carbon material powder;
3) Mixing the carbon material powder obtained in the step 2) with nano alumina, adding the mixture into a sodium hydroxide aqueous solution, carrying out ultrasonic treatment, drying, then transferring into a furnace for high-temperature calcination, cooling, and grinding to obtain mixed powder;
4) And heating and ultrasonic treatment is carried out on the obtained mixed powder, polyphenyl and hexabenzol in pyridine, the mixture obtained by evaporating the pyridine is mixed and ground with phenolic resin, and the aluminum-carbon coated graphite anode material for the lithium ion battery is obtained after solidification and carbonization.
As a further improvement of the technical scheme, the high-temperature calcination temperature in the step 1) is 950 ℃, the high-temperature calcination temperature in the step 2) is 800-850 ℃, and the high-temperature calcination temperature in the step 3) is 750-850 ℃, and the high-temperature calcination is carried out in an inert atmosphere.
As a further improvement of the technical scheme, the heating rate of the high-temperature calcination is controlled to be 1-2 ℃/min; the cooling rate is controlled to be 6-8 ℃/min.
According to the invention, a small amount of needle coke which is calcined in advance and is used for regulating graphitization and porosity is doped into natural graphite powder, the powder obtained by adding the mixed needle coke and the powder into concentrated sulfuric acid for ultrasonic treatment is used as a basic carbon material, the basic carbon material is coated with nano alumina in sodium hydroxide, the calcined mixed powder is further coated with polyphenyl and hexabenzobenzene through heating ultrasonic reaction, and finally the aluminum carbon coated graphite anode material is obtained through solidifying and carbonizing with phenolic resin. According to the invention, calcined acicular Jiao Canza natural graphite is used as a carbon material, nano aluminum oxide, polyphenyl and hexabenzol are further selected to double-coat the carbon material, and the aluminum oxide layer coating is combined with the polyphenyl and hexabenzol coating, so that the electron flow of the electrode can be improved, the voltage hysteresis phenomenon in the initial stage of discharge is effectively inhibited, and the safety performance of the battery is improved. The inventor researches and discovers that when the mixed powder obtained by calcining the nano alumina coated basic carbon material, the polyphenyl and hexabenzobenzene are mixed according to the mass ratio of (2-3) to (3-5) to prepare the aluminum-carbon double-coating layer, the battery can keep the original higher discharge performance and cycle performance at a lower temperature, and the preparation ratio of the aluminum-carbon double-coating layer is changed, although the discharge cycle performance at the normal temperature of the battery is not greatly influenced, the discharge, particularly the cycle performance, of the battery is greatly reduced under the low temperature condition, and the lower temperature is more obvious.
As a further improvement of the technical scheme, the particle sizes of the coke powder, the natural graphite powder, the carbon material powder and the mixed powder are controlled within the range of 0.1-10 mu m.
As a further improvement of the technical scheme, the mass ratio of the coke powder to the natural graphite powder in the step 2) is1 (1.5-4.5), the solid-liquid ratio of the coke powder to the natural graphite powder is 1:20, and the mass fraction of the concentrated sulfuric acid is 90%.
As a further improvement of the technical scheme, the mass ratio of the carbon material powder to the nano alumina in the step 3) is 10 (1.5-3.0), the solid-liquid ratio of the carbon material powder to the nano alumina is 1:20, and the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L.
As a further improvement of the technical scheme, the mass ratio of the mixed powder in the step 4) to the polyphenyl and hexabenzol is 12 (2-3) to 3-5.
As a further improvement of the above technical solution, step 4) the curing and carbonizing operations are as follows: mixing the mixture with phenolic resin according to the mass ratio of (7.5-15): 1, grinding, and then curing and carbonizing successively: the curing temperature is 420-450 ℃, the heat preservation is 2-3 h, the carbonization temperature is 1010-1060 ℃ and the heat preservation is 3-4 h.
Compared with the prior art, the invention has the beneficial effects that:
1. The aluminum-carbon coated graphite anode material prepared by the process method can effectively inhibit voltage hysteresis, and improves the use safety.
2. The lithium ion battery assembled by the aluminum-carbon coated graphite anode material prepared by the process method has higher initial capacity and excellent cycle performance, and the capacity retention rate of the lithium ion battery in 500 cycles is close to 80% under the use condition of lower temperature, so that the defect of the graphite anode material prepared by the conventional process is effectively overcome, and the lithium ion battery has good market competitiveness.
3. The process method is simple to operate, easy to control and suitable for industrial production.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described in the following examples. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
Aluminum-carbon coated graphite anode material for lithium ion battery:
1. pulverizing needle coke, calcining in a nitrogen-protected calciner at high temperature (1.5deg.C/min for 60 min at 950 deg.C, cooling to room temperature at 7.5deg.C/min), and grinding to obtain coke powder.
2. Mixing coke powder and natural graphite powder according to a mass ratio of 1:4, adding into concentrated sulfuric acid (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 80W and drying the mixture after 10: 10min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating at 1.5 ℃/min to 840 ℃, preserving heat for 60 min, and cooling to room temperature at 7.5 ℃/min), and grinding the mixture to obtain carbon material powder.
3. Mixing carbon material powder and nano aluminum oxide according to the mass ratio of 10:2.4, adding into 0.1 mol/L sodium hydroxide aqueous solution (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 120: 120W, drying the mixture after 15: 15 min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating to 1.5 ℃/min, preserving heat for 60 min after heating to 820 ℃, and cooling to room temperature by 7.5 ℃/min), and grinding the mixture to obtain mixed powder.
4. And (3) carrying out ultrasonic treatment (65 ℃ C., 70W, 30 min) on the mixed powder, polyphenyl and hexabenzol in pyridine according to a mass ratio of 12:3:4.5, evaporating the pyridine to obtain a mixture, mixing and grinding the mixture with phenolic resin according to a mass ratio of 9.5:1, curing at 435 ℃, preserving heat for 2.5 h, carbonizing at 1040 ℃ and preserving heat for 3.5 h to obtain the aluminum-carbon coated graphite anode material for the lithium ion battery.
And (3) performance detection: the battery (PP film is an isolating film) is assembled by taking aluminum sheet/lithium manganate as an anode, copper sheet/the anode material of the embodiment as an anode, propylene carbonate, dimethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1 as electrolyte, and the charging and discharging tests under different temperature environments are carried out, and the results are as follows:
the first discharge efficiency was 95.6%.
20 ℃ C: gram capacity 441 mAh/g, cycle 500 week capacity 412 mAh/g (1C); -10 ℃: gram capacity 424 mAh/g, cyclic 500 week capacity 388 mAh/g (1C); -40 ℃: gram capacity 393 mAh/g, cycle 500 week capacity 329 mAh/g (1C).
Example 2
Aluminum-carbon coated graphite anode material for lithium ion battery:
1. pulverizing needle coke, calcining in a nitrogen-protected calciner at high temperature (1.5deg.C/min for 60 min at 950 deg.C, cooling to room temperature at 7.5deg.C/min), and grinding to obtain coke powder.
2. Mixing coke powder and natural graphite powder according to a mass ratio of 1:2, adding into concentrated sulfuric acid (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 80W and drying the mixture after 10: 10min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating at 1.5 ℃/min to 820 ℃ and then preserving heat for 60 min, cooling at 7.5 ℃/min to room temperature), and grinding the mixture to obtain carbon material powder.
3. Mixing carbon material powder and nano aluminum oxide according to the mass ratio of 10:1.5, adding into 0.1 mol/L sodium hydroxide aqueous solution (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 120: 120W, drying the mixture after 15: 15 min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating at 1.5 ℃/min to 780 ℃, preserving heat for 60 min, and cooling at 7.5 ℃/min to room temperature), and grinding the mixture to obtain mixed powder.
4. And (3) carrying out ultrasonic treatment (65 ℃ C., 70W, 30 min) on the mixed powder, polyphenyl and hexabenzol in pyridine according to a mass ratio of 12:3:4.5, evaporating the pyridine to obtain a mixture, mixing and grinding the mixture with phenolic resin according to a mass ratio of 9.5:1, curing at 435 ℃, preserving heat for 2.5 h, carbonizing at 1040 ℃ and preserving heat for 3.5 h to obtain the aluminum-carbon coated graphite anode material for the lithium ion battery.
And (3) performance detection: the battery (PP film is an isolating film) is assembled by taking aluminum sheet/lithium manganate as an anode, copper sheet/the anode material of the embodiment as an anode, propylene carbonate, dimethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1 as electrolyte, and the charging and discharging tests under different temperature environments are carried out, and the results are as follows:
The first discharge efficiency was 93.9%.
20 ℃ C: gram capacity 421 mAh/g, cycle 500 week capacity 390 mAh/g (1C); -10 ℃: gram capacity 403 mAh/g, cycle 500 week capacity 364 mAh/g (1C); -40 ℃: gram capacity 372 mAh/g, cycle 500 week capacity 305 mAh/g (1C).
Example 3
Aluminum-carbon coated graphite anode material for lithium ion battery:
1. pulverizing needle coke, calcining in a nitrogen-protected calciner at high temperature (1.5deg.C/min for 60 min at 950 deg.C, cooling to room temperature at 7.5deg.C/min), and grinding to obtain coke powder.
2. Mixing coke powder and natural graphite powder according to a mass ratio of 1:4, adding into concentrated sulfuric acid (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 80W and drying the mixture after 10: 10min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating at 1.5 ℃/min to 840 ℃, preserving heat for 60 min, and cooling to room temperature at 7.5 ℃/min), and grinding the mixture to obtain carbon material powder.
3. Mixing carbon material powder and nano aluminum oxide according to the mass ratio of 10:2.4, adding into 0.1 mol/L sodium hydroxide aqueous solution (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 120: 120W, drying the mixture after 15: 15 min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating to 1.5 ℃/min, preserving heat for 60 min after heating to 820 ℃, and cooling to room temperature by 7.5 ℃/min), and grinding the mixture to obtain mixed powder.
4. And (3) carrying out ultrasonic treatment (65 ℃, 70W, 30 min) on the mixed powder, polyphenyl and hexabenzol in pyridine according to a mass ratio of 12:2:5, evaporating the pyridine to obtain a mixture, mixing and grinding the mixture with phenolic resin according to a mass ratio of 7.5:1, curing at 420 ℃, preserving heat for 3h, carbonizing at 1010 ℃, and preserving heat for 4 h to obtain the aluminum-carbon coated graphite anode material for the lithium ion battery.
And (3) performance detection: the battery (PP film is an isolating film) is assembled by taking aluminum sheet/lithium manganate as an anode, copper sheet/the anode material of the embodiment as an anode, propylene carbonate, dimethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1 as electrolyte, and the charging and discharging tests under different temperature environments are carried out, and the results are as follows:
The first discharge efficiency was 93.2%.
20 ℃ C: gram capacity 404 mAh/g, cycle 500 week capacity 371 mAh/g (1C); -10 ℃: gram capacity 375 mAh/g, cycle 500 weeks capacity 337 mAh/g (1C); -40 ℃: gram capacity 341 mAh/g, cycle 500 week capacity 276 mAh/g (1C).
Example 4
Aluminum-carbon coated graphite anode material for lithium ion battery:
1. pulverizing needle coke, calcining in a nitrogen-protected calciner at high temperature (1.5deg.C/min for 60 min at 950 deg.C, cooling to room temperature at 7.5deg.C/min), and grinding to obtain coke powder.
2. Mixing coke powder and natural graphite powder according to a mass ratio of 1:4, adding into concentrated sulfuric acid (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 80W and drying the mixture after 10: 10min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating at 1.5 ℃/min to 840 ℃, preserving heat for 60 min, and cooling to room temperature at 7.5 ℃/min), and grinding the mixture to obtain carbon material powder.
3. Mixing carbon material powder and nano aluminum oxide according to the mass ratio of 10:2.4, adding into 0.1 mol/L sodium hydroxide aqueous solution (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 120: 120W, drying the mixture after 15: 15 min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating to 1.5 ℃/min, preserving heat for 60 min after heating to 820 ℃, and cooling to room temperature by 7.5 ℃/min), and grinding the mixture to obtain mixed powder.
4. And (3) carrying out ultrasonic treatment (65 ℃, 70W, 30 min) on the mixed powder, polyphenyl and hexabenzol in pyridine according to a mass ratio of 12:3:3, evaporating the pyridine to obtain a mixture, mixing and grinding the mixture with phenolic resin according to a mass ratio of 12.5:1, curing at 435 ℃, preserving heat for 2.5 hours, carbonizing at 1040 ℃, and preserving heat for 3.5 h to obtain the aluminum-carbon coated graphite anode material for the lithium ion battery.
And (3) performance detection: the battery (PP film is an isolating film) is assembled by taking aluminum sheet/lithium manganate as an anode, copper sheet/the anode material of the embodiment as an anode, propylene carbonate, dimethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1 as electrolyte, and the charging and discharging tests under different temperature environments are carried out, and the results are as follows:
The first discharge efficiency was 94.8%.
20 ℃ C: gram capacity 426 mAh/g, cycle 500 week capacity 394 mAh/g (1C); -10 ℃: gram capacity 405 mAh/g, cycle 500 week capacity 368 mAh/g (1C); -40 ℃: gram capacity 366 mAh/g, cycle 500 week capacity 296 mAh/g (1C).
Comparative example 1
1. Pulverizing needle coke, calcining in a nitrogen-protected calciner at high temperature (1.5deg.C/min for 60 min at 950 deg.C, cooling to room temperature at 7.5deg.C/min), and grinding to obtain coke powder.
2. Mixing coke powder and natural graphite powder according to a mass ratio of 1:4, adding into concentrated sulfuric acid (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 80W and drying the mixture after 10: 10min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating at 1.5 ℃/min to 840 ℃, preserving heat for 60 min, and cooling to room temperature at 7.5 ℃/min), and grinding the mixture to obtain carbon material powder.
3. Carrying out ultrasonic treatment (65 ℃ C., 70W, 30 min) on carbon material powder, polyphenyl and hexabenzol in pyridine according to a mass ratio of 12:3:4.5, evaporating pyridine to obtain a mixture, mixing and grinding the mixture with phenolic resin according to a mass ratio of 9.5:1, curing at 435 ℃, preserving heat for 2.5 h, carbonizing at 1040 ℃ and preserving heat for 3.5 h to obtain the graphite cathode material for the lithium ion battery.
And (3) performance detection: the battery (PP film is an isolating film) is assembled by taking an aluminum sheet/lithium manganate as an anode, taking a copper sheet/the cathode material of the comparative example as a cathode, taking propylene carbonate, dimethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1 as electrolyte, and carrying out charge and discharge tests under different temperature environments, wherein the results are as follows:
The first discharge efficiency was 92.9%.
20 ℃ C: gram capacity 441 mAh/g, cycle 500 week capacity 412 mAh/g (1C); -10 ℃: gram capacity 377 mAh/g, cycle 500 week capacity 290 mAh/g (1C); -40 ℃: gram capacity 211 mAh/g, cycle 500 week capacity 94 mAh/g (1C).
Comparative example 2
1. Pulverizing needle coke, calcining in a nitrogen-protected calciner at high temperature (1.5deg.C/min for 60 min at 950 deg.C, cooling to room temperature at 7.5deg.C/min), and grinding to obtain coke powder.
2. Mixing coke powder and natural graphite powder according to a mass ratio of 1:4, adding into concentrated sulfuric acid (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 80W and drying the mixture after 10: 10min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating at 1.5 ℃/min to 840 ℃, preserving heat for 60 min, and cooling to room temperature at 7.5 ℃/min), and grinding the mixture to obtain carbon material powder.
3. Mixing carbon material powder and nano aluminum oxide according to the mass ratio of 10:2.4, adding into 0.1 mol/L sodium hydroxide aqueous solution (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 120: 120W, drying the mixture after 15: 15 min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating to 1.5 ℃/min, preserving heat for 60 min after heating to 820 ℃, and cooling to room temperature by 7.5 ℃/min), and grinding the mixture to obtain mixed powder.
4. Mixing and grinding the mixed powder with phenolic resin according to the mass ratio of 9.5:1, curing at 435 ℃, preserving heat for 2.5 h, carbonizing at 1040 ℃ and preserving heat for 3.5 h to obtain the graphite cathode material for the lithium ion battery.
And (3) performance detection: the battery (PP film is an isolating film) is assembled by taking an aluminum sheet/lithium manganate as an anode, taking a copper sheet/the cathode material of the comparative example as a cathode, taking propylene carbonate, dimethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1 as electrolyte, and carrying out charge and discharge tests under different temperature environments, wherein the results are as follows:
The first discharge efficiency was 86.6%.
20 ℃ C: gram capacity 349 mAh/g, cycle 500 week capacity 258 mAh/g (1C); -10 ℃: gram capacity 227 mAh/g, cycle 500 week capacity 72 mAh/g (1C); -40 ℃: gram capacity 56 mAh/g, cycle 60 week capacity 0 (1C).
Comparative example 3
1. Pulverizing needle coke, calcining in a nitrogen-protected calciner at high temperature (1.5deg.C/min for 60 min at 950 deg.C, cooling to room temperature at 7.5deg.C/min), and grinding to obtain coke powder.
2. Mixing coke powder and natural graphite powder according to a mass ratio of 1:4, adding into concentrated sulfuric acid (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 80W and drying the mixture after 10: 10min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating at 1.5 ℃/min to 840 ℃, preserving heat for 60 min, and cooling to room temperature at 7.5 ℃/min), and grinding the mixture to obtain carbon material powder.
3. Mixing carbon material powder and nano aluminum oxide according to the mass ratio of 10:2.4, adding into 0.1 mol/L sodium hydroxide aqueous solution (solid-liquid ratio of 1:20, g/mL), carrying out ultrasonic treatment on the mixture by 120: 120W, drying the mixture after 15: 15 min, transferring the mixture into a nitrogen-protected calciner for high-temperature calcination (heating to 1.5 ℃/min, preserving heat for 60 min after heating to 820 ℃, and cooling to room temperature by 7.5 ℃/min), and grinding the mixture to obtain mixed powder.
4. And (3) carrying out ultrasonic treatment (65 ℃, 70W, 30 min) on the mixed powder, polyphenyl and hexabenzol in pyridine according to a mass ratio of 12:5:1, evaporating the pyridine to obtain a mixture, mixing and grinding the mixture with phenolic resin according to a mass ratio of 9.5:1, curing at 435 ℃, preserving heat for 2.5 h, carbonizing at 1040 ℃, and preserving heat for 3.5 h to obtain the graphite anode material for the lithium ion battery.
And (3) performance detection: the battery (PP film is an isolating film) is assembled by taking an aluminum sheet/lithium manganate as an anode, taking a copper sheet/the cathode material of the comparative example as a cathode, taking propylene carbonate, dimethyl carbonate and methyl ethyl carbonate with the volume ratio of 1:1:1 as electrolyte, and carrying out charge and discharge tests under different temperature environments, wherein the results are as follows:
The first discharge efficiency was 93.5%.
20 ℃ C: gram capacity 443 mAh/g, cycle 500 week capacity 415 mAh/g (1C); -10 ℃: gram capacity 420 mAh/g, cyclic 500 week capacity 249 mAh/g (1C); -40 ℃: gram capacity 391 mAh/g, cycle 500 weeks capacity 142 mAh/g (1C).
As shown by the detection data results of the embodiment, the lithium ion battery prepared from the aluminum-carbon coated graphite anode material has the advantages of good first efficiency, large capacity and good cycle performance, and can maintain higher discharge efficiency and cycle performance at a lower temperature. Comparing the detection results of the embodiment 1 and the comparative example 1 of the invention, the first discharge efficiency, capacity and cycle performance of the lithium ion battery assembled by the graphite anode material prepared by coating without adding nano alumina are not obvious, the battery capacity is reduced slightly at-10 ℃ and the cycle performance is obviously reduced, and the capacity is lower than 50% at-40 ℃. Comparing the detection results of the embodiment 1 and the comparative example 2 of the invention, the first discharge efficiency, capacity and cycle performance of the lithium ion battery assembled by the graphite anode material prepared by coating without adding polyphenyl or hexabenzol are obviously reduced, and the performance deterioration is more obvious under the low-temperature condition. Comparing the detection results of the embodiment 1 and the comparative example 2 of the invention, it is known that the first discharge efficiency, the capacity at normal temperature, the cycle performance at normal temperature and the capacity at low temperature of the lithium ion battery assembled by the graphite anode material prepared by coating the mixed powder, the polyphenyl and the hexabenzol outside the preferred mass ratio range can be kept at higher levels, but the cycle performance at low temperature is remarkably reduced to different degrees.
The lithium ion batteries prepared in examples 1 to 4 and comparative examples 1 to 3 were respectively subjected to a 0.2C discharge test, and the voltage hysteresis was reduced by about 0.58V, 0.55V, 0.53V, 0.56V,0.17V, 0.24V, 0.52V, respectively, as compared to the lithium ion battery prepared by using untreated natural graphite as the negative electrode; the 1C discharge test voltage hysteresis was reduced by about 0.63V, 0.61V, 0.59V, 0.63V,0.21V, 0.28V, 0.60V, respectively. Therefore, the voltage hysteresis of the lithium ion battery prepared from the aluminum-carbon coated graphite anode material prepared by the invention in the initial stage of discharge is obviously improved, and the effect is more obvious when the discharge rate is higher.
The embodiments described above represent only a few preferred embodiments of the present invention, which are described in more detail and are not intended to limit the present invention. It should be noted that various changes and modifications can be made to the present invention by those skilled in the art, and any modifications, equivalent substitutions, improvements, etc. which are within the spirit and principle of the present invention are included in the scope of the present invention.
Claims (5)
1. The preparation method of the aluminum-carbon coated graphite anode material for the lithium ion battery is characterized by comprising the following steps of:
1) Pulverizing needle coke, calcining at high temperature in a furnace, cooling, and grinding into coke powder;
2) Mixing the coke powder obtained in the step 1) with natural graphite powder, adding the mixture into concentrated sulfuric acid, carrying out ultrasonic treatment, drying, then transferring into a furnace, calcining at high temperature, cooling, and grinding to obtain carbon material powder;
3) Mixing the carbon material powder obtained in the step 2) with nano alumina, adding the mixture into a sodium hydroxide aqueous solution, carrying out ultrasonic treatment, drying, then transferring into a furnace for high-temperature calcination, cooling, and grinding to obtain mixed powder;
4) Heating and ultrasonic treatment is carried out on the mixed powder obtained in the step 3) and polyphenyl and hexabenzol in pyridine, the mixture obtained by evaporating the pyridine is mixed and ground with phenolic resin, and the aluminum-carbon coated graphite anode material for the lithium ion battery is obtained after solidification and carbonization;
The high-temperature calcination temperature in the step 1) is 950 ℃, the high-temperature calcination temperature in the step 2) is 800-850 ℃, and the high-temperature calcination temperature in the step 3) is 750-850 ℃, wherein the high-temperature calcination is carried out in an inert atmosphere;
The mass ratio of the carbon material powder to the nano alumina in the step 3) is 10 (1.5-3.0), the solid-liquid ratio of the carbon material powder to the nano alumina is 1:20, and the concentration of the sodium hydroxide aqueous solution is 0.1 mol/L;
The mass ratio of the mixed powder to the polyphenyl and hexabenzol in the step 4) is 12 (2-3) (3-5); the concrete operations of curing and carbonization are as follows: mixing the mixture with phenolic resin according to the mass ratio of 1 (7.5-15), grinding, and then curing and carbonizing successively: the curing temperature is 420-450 ℃, the heat preservation is 2-3 h, the carbonization temperature is 1010-1060 ℃ and the heat preservation is 3-4 h.
2. The method for preparing an aluminum-carbon coated graphite negative electrode material for a lithium ion battery according to claim 1, wherein the heating rate of the high-temperature calcination in steps 1) to 3) is controlled to be 1-2 ℃/min; the cooling rate of the cooling in the steps 1) to 3) is controlled to be 6-8 ℃/min.
3. The method for preparing an aluminum-carbon coated graphite negative electrode material for a lithium ion battery according to claim 1, wherein the particle sizes of the coke powder, the natural graphite powder, the carbon material powder and the mixed powder are controlled within the range of 0.1-10 μm.
4. The preparation method of the aluminum-carbon coated graphite negative electrode material for the lithium ion battery, which is characterized in that in the step 2), the mass ratio of the coke powder to the natural graphite powder is1 (1.5-4.5), and the solid-liquid ratio of the coke powder to the natural graphite powder is 1:20.
5. The aluminum-carbon coated graphite anode material for lithium ion batteries, which is prepared by the preparation method according to any one of claims 1-4.
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