CN112490394B - Chemical prelithiation method for graphite electrode of lithium ion battery - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 62
- 239000010439 graphite Substances 0.000 title claims abstract description 62
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000126 substance Substances 0.000 title claims abstract description 18
- -1 anion free radical Chemical class 0.000 claims abstract description 45
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 35
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 19
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021382 natural graphite Inorganic materials 0.000 claims description 7
- 239000007773 negative electrode material Substances 0.000 claims description 5
- WNSPFMGXOCUATQ-UHFFFAOYSA-N 2,2-diethyloxolane Chemical compound CCC1(CC)CCCO1 WNSPFMGXOCUATQ-UHFFFAOYSA-N 0.000 claims description 4
- IHMXVSZXHFTOFN-UHFFFAOYSA-N 2-ethyloxolane Chemical compound CCC1CCCO1 IHMXVSZXHFTOFN-UHFFFAOYSA-N 0.000 claims description 4
- TZYYJCQVZHDEMI-UHFFFAOYSA-N 2-phenyloxolane Chemical compound C1CCOC1C1=CC=CC=C1 TZYYJCQVZHDEMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 claims description 4
- DKKJMZRYRPJLME-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3C=CC12.[Li] Chemical compound C1=CC=CC=2C3=CC=CC=C3C=CC12.[Li] DKKJMZRYRPJLME-UHFFFAOYSA-N 0.000 claims description 3
- UENPGSSYCLIBMR-UHFFFAOYSA-N anthracene;lithium Chemical compound [Li].C1=CC=CC2=CC3=CC=CC=C3C=C21 UENPGSSYCLIBMR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- GBVSONMCEKNESD-UHFFFAOYSA-N 1,1'-biphenyl;lithium Chemical compound [Li].C1=CC=CC=C1C1=CC=CC=C1 GBVSONMCEKNESD-UHFFFAOYSA-N 0.000 claims description 2
- SYHYMQPZTOVLRI-UHFFFAOYSA-N CC1=CC=C(C=C1)C1=CC=C(C=C1)C.[Li] Chemical compound CC1=CC=C(C=C1)C1=CC=C(C=C1)C.[Li] SYHYMQPZTOVLRI-UHFFFAOYSA-N 0.000 claims description 2
- PXXRRQOFRCDQHK-UHFFFAOYSA-N CC1=CC=CC2=CC=CC=C12.[Li] Chemical compound CC1=CC=CC2=CC=CC=C12.[Li] PXXRRQOFRCDQHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- WVEGUTLWOIFKDF-UHFFFAOYSA-N [Li].C1=CC2=CC=C3C=CC=C4C=CC(=C1)C2=C34 Chemical compound [Li].C1=CC2=CC=C3C=CC=C4C=CC(=C1)C2=C34 WVEGUTLWOIFKDF-UHFFFAOYSA-N 0.000 claims description 2
- ZAOAMYDIAMQNIO-UHFFFAOYSA-N [Li].CC1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound [Li].CC1=C(C=CC=C1)C1=CC=CC=C1 ZAOAMYDIAMQNIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000005087 graphitization Methods 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 238000009830 intercalation Methods 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 150000003254 radicals Chemical class 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229910013872 LiPF Inorganic materials 0.000 description 7
- 101150058243 Lipf gene Proteins 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 5
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YGZQJYIITOMTMD-UHFFFAOYSA-N 1-propoxybutane Chemical compound CCCCOCCC YGZQJYIITOMTMD-UHFFFAOYSA-N 0.000 description 3
- DMUSSSYUUUYJRM-UHFFFAOYSA-N 1-propoxypentane Chemical compound CCCCCOCCC DMUSSSYUUUYJRM-UHFFFAOYSA-N 0.000 description 3
- VDMXPMYSWFDBJB-UHFFFAOYSA-N 1-ethoxypentane Chemical compound CCCCCOCC VDMXPMYSWFDBJB-UHFFFAOYSA-N 0.000 description 2
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 2
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 2
- DBUJFULDVAZULB-UHFFFAOYSA-N 1-methoxypentane Chemical compound CCCCCOC DBUJFULDVAZULB-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
- H01M4/625—Carbon or graphite
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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
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Abstract
The invention discloses a chemical prelithiation method of a graphite electrode of a lithium ion battery, which comprises the following steps: dissolving lithiation reagent containing anion free radical in monobasic ether to obtain lithiation reagent solution with concentration of 0.001-10 mol/L; and (3) carrying out contact reaction on the prepared graphite negative plate of the lithium ion battery and a lithiation reagent solution for 1s-48h, washing and drying to obtain the pre-lithiated graphite electrode. According to the method, the free radical anion lithiation reagent with mild property is selected, and the graphite cathode material of the lithium ion battery is chemically pre-lithiated under a relatively safe chemical environment, so that the first cycle efficiency of the graphite electrode is improved, and the energy density of the whole battery is further improved. The used monoether solvent is compatible with the graphite cathode, and the phenomena of destroying the electrochemical performance of the graphite cathode such as co-intercalation or stripping can not occur; the solution system has strong reducibility and rapid lithiation process, and does not influence the electrochemical performance of the electrode.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a chemical pre-lithiation method for a graphite electrode of a lithium ion battery.
Background
The lithium ion battery has the advantages of high specific energy, large volume energy density, low self-discharge performance, long service life and the like, and is widely applied to the fields of 3C, electric automobiles and the like. Over the past 20 years, many important breakthroughs have been made in the research on energy density, cost, safety and the like of lithium ion batteries, and now the energy density of lithium ion batteries has increased to reach or approach the limit value of the existing electrode materials. In the current commercial lithium ion battery, the first cycle coulombic efficiency of the positive electrodes such as Lithium Cobaltate (LCO) and lithium iron phosphate (LFP) is more than 95 percent, and the lithium ion battery is an active lithium ion source; while the first cycle efficiency of graphite cathodes is low (< 90%), it consumes active lithium ions, which affects the energy density of the battery. Therefore, it is imperative to improve the first cycle efficiency of graphite cathodes.
Prelithiation refers to storing a certain amount of active lithium in the electrode prior to the battery charge-discharge cycle to offset the first week of irreversible loss. This is an effective way to improve the first cycle efficiency of the cell. The current prelithiation method for graphite anodes includes: in Journal of Power Sources (2014,260, 57-61), Wang et al used Stabilized Lithium Metal Powder (SLMP) in graphite negative electrodes to compensate for the capacity loss of the graphite negative electrode in the first week; in another Journal of Power Sources (2018,378,522-526.) Holtstiege et al use thin lithium metal foil that is internally shorted to the graphite anode in the electrolyte to embed lithium in advance; LG 104584278A of co-ltd, pre-lithiation was performed by charging a lithium metal plate by placing a pole piece in a reaction tank; tianjin Bamo science co ltd patent 104538591a prelithiates the negative electrode with lithium metal. However, the above prelithiation methods all have problems such as complicated process, harsh preparation conditions and poor operability. Such as lithium powder and lithium foil, are highly reactive and require strict control of the water oxygen value in the environment or polymer coating for air isolation, which undoubtedly increases the cost. The chemical prelithiation method has the advantages of cheap and easily obtained reagents, stability, safety and easy industrialization. However, the commonly used reagent ethylene glycol dimethyl ether (DME) of the currently developed chemical lithiation reagent is not compatible with the graphite cathode, and the co-intercalation phenomenon can damage the structure of the graphite cathode and influence the electrochemical performance of the graphite cathode. On the other hand, graphite electrodes have low intercalation potentials (<0.2V), and it is generally difficult to prelithiate graphite negative electrodes with conventional lithiation reagents such as lithium naphthalene (0.38V). In summary, there is currently no mature and well operable chemical prelithiation method for prelithiating graphite anodes.
Disclosure of Invention
The invention provides a chemical pre-lithiation method of a graphite electrode of a lithium ion battery, aiming at the problem that the first cycle efficiency of a matched full battery of the conventional commercial lithium ion battery is influenced due to low first cycle efficiency of a graphite cathode material, so that the energy density of the lithium ion battery is further influenced, the first cycle efficiency of the graphite electrode is improved, and the possibility is provided for the development of a series of battery systems with high first cycle efficiency and high energy density.
In order to achieve the purpose, the technical scheme is as follows:
the chemical prelithiation method for graphite electrode of lithium ion battery includes the following steps:
dissolving lithiation reagent containing anion free radical in monobasic ether to obtain lithiation reagent solution with concentration of 0.001-10 mol/L;
and (3) carrying out contact reaction on the prepared graphite negative plate of the lithium ion battery and a lithiation reagent solution for 1s-48h, washing and drying to obtain the pre-lithiated graphite electrode.
According to the scheme, the graphite negative electrode sheet is prepared from the following components in parts by weight: 70-99 parts of graphite negative electrode active material, 0.5-20 parts of conductive agent and 0.5-10 parts of adhesive.
According to the scheme, the graphite negative electrode active material is one or a mixture of natural graphite, artificial graphite, modified graphite and a carbon material with high graphitization degree.
According to the scheme, the conductive agent is one or a mixture of acetylene black, Ketjen black, Super P, MCMB and carbon nano tubes.
According to the scheme, the binder is one or a mixture of PVDF, CMC, PAA and SBR.
According to the scheme, the monoether is one or a mixture of methyl propyl ether, methyl butyl ether, methyl amyl ether, ethyl propyl ether, ethyl butyl ether, ethyl amyl ether, propyl butyl ether, propyl amyl ether, tetrahydrofuran, methyl tetrahydrofuran, dimethyl tetrahydrofuran, ethyl tetrahydrofuran, diethyl tetrahydrofuran and phenyl tetrahydrofuran.
According to the scheme, the lithiation reagent containing the anion free radical is one or a mixture of naphthalene lithium, methylnaphthalene lithium, dimethylnaphthalene lithium, tetramethylnaphthalene lithium, anthracene lithium, methylanthracene lithium, dimethylanthracene lithium, tetramethylanthracene lithium, phenanthrene lithium, methylpheny lithium, trimethylphenanthrene lithium, tetramethylphenanthrene lithium, pyrene lithium, methylpyrene lithium, dimethylpyrene lithium, trimethylpyrene lithium, tetramethylpyrene lithium, perylene lithium, methylperylene lithium, dimethylperylene lithium, trimethylperylene lithium, tetramethylperylene lithium, biphenyl lithium, methylbiphenyl lithium, dimethylbiphenyl lithium and tetramethylbiphenyl lithium.
According to the scheme, the washing solvent is one or a mixture of methyl propyl ether, methyl butyl ether, methyl amyl ether, ethyl propyl ether, ethyl butyl ether, ethyl amyl ether, propyl butyl ether, propyl amyl ether, tetrahydrofuran, methyl tetrahydrofuran, dimethyl tetrahydrofuran, ethyl tetrahydrofuran, diethyl tetrahydrofuran, phenyl tetrahydrofuran and carbonic ester.
According to the scheme, the concentration of the lithiation reagent solution is preferably 0.01-5 mol/L.
According to the scheme, the preferable contact reaction time is 10s-24 h.
The graphite electrode obtained by the invention is a full battery with a negative electrode, and the positive electrode of the full battery can be lithium cobaltate, lithium iron phosphate, lithium-rich manganese base, high nickel ternary, other metal oxides, sulfur electrode and other lithium ion battery positive electrode materials or one or more of the materials.
Compared with the prior art, the invention has the following beneficial effects:
according to the method, the free radical anion lithiation reagent with mild property is selected, and the graphite cathode material of the lithium ion battery is chemically pre-lithiated under a relatively safe chemical environment, so that the first cycle efficiency of the graphite electrode is improved, and the energy density of the whole battery is further improved. The used monoether solvent is compatible with the graphite cathode, and the phenomena of destroying the electrochemical performance of the graphite cathode such as co-intercalation or stripping can not occur; the solution system has strong reducibility and a fast lithiation process, and does not influence the electrochemical performance of the electrode;
the method is a normal-temperature reaction, has simple process, controllable lithiation depth and strong safety, and is easy for industrialization.
The pre-lithiated graphite cathode is matched with the anode, so that the energy density and the cycling stability of the whole battery are improved, and a lithium ion battery system which is more consistent with market expectation is obtained.
Drawings
FIG. 1: XRD patterns of the natural graphite electrode of example 1 after prelithiation at different depths.
FIG. 2: the natural graphite electrode of example 1 was prelithiated with charge and discharge curves at different depths.
FIG. 3: the first two-week charge-discharge curves before and after prelithiation of the artificial graphite electrode of example 2.
FIG. 4: cycling profiles before and after prelithiation of the artificial graphite electrode of example 2.
FIG. 5: the charge-discharge curve of the full cell matched with the lithium iron phosphate positive electrode before and after the artificial graphite electrode of example 2 is prelithiated.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
(1) 1mL of 0.5mol/L naphthalene lithium methyl propyl ether solution is taken to react with a natural graphite electrode (the loading amount is about 2mg and the graphite content is 93 wt%) under the protection of inert atmosphere for different time (5min, 30min, 1h and 3 h). After the reaction is completed, washing the mixture for three times by using methyl propyl ether, and drying the mixture for later use.
(2) XRD detection is carried out on the graphite electrodes with different lithiation depths, the scanning speed is 4 DEG/min, and the XRD pattern is shown in figure 1, and the prelithiation depth of the graphite electrode is gradually deepened along with the increase of time, and even the graphite electrode can be lithiated to first-order graphite (LiC)6)。
(3) Respectively using natural graphite electrodes with different prelithiation depths as positive electrodes and lithium metal as negative electrode, and using ternary electrolyte (1M LiPF)6EC/DEC/DMC (v: v: v ═ 1:1:1)) half cells were assembled and subjected to charge and discharge tests. The charging and discharging curve of the first week is shown in figure 2, as the lithiation degree is deepened, the open-circuit voltage is gradually reduced, the discharging voltage is gradually reduced, and the charging voltage is kept unchanged, which shows that the lithiation reagent does not influence the natural graphite while successfully pre-lithiating the natural graphiteThe inverse capacity.
Example 2
(1) 3mL of 0.25mol/L ethyl butyl ether solution of tetramethyl biphenyl lithium is reacted with an artificial graphite electrode (the loading is about 2.5mg and the graphite content is 95 wt%) for 2 minutes under the protection of inert atmosphere. After the reaction is completed, washing the mixture for three times by using dimethyl carbonate, and drying the mixture for later use.
(2) Respectively using artificial graphite electrodes before and after pre-lithiation as positive electrodes and lithium metal as negative electrodes, and using ternary electrolyte (1M LiPF)6EC/DEC/DMC (v: v: v ═ 1:1:1)) half cells were assembled and subjected to charge and discharge tests. The charge and discharge curves and cycle diagrams of the first two weeks are shown in fig. 3 and 4, after pre-lithiation, the open-circuit voltage of the half-cell is reduced from 3.01V to 0.23V, and the first-week efficiency is improved from 84.45% to 98.91%. And the efficiency of the artificial graphite after the prelithiation is improved more quickly during circulation, and the circulation stability is better.
(3) Using artificial graphite electrodes before and after pre-lithiation as negative electrodes, using lithium iron phosphate as positive electrodes (the mass ratio of the positive and negative active materials is about 1:1.05), and using a ternary electrolyte (1M LiPF)6EC/DEC/DMC (v: v: v ═ 1:1:1)) was assembled into a full cell, and a charge-discharge test was performed. The charging and discharging curve of the first week is shown as 5, the full battery matched with the pre-lithiated graphite electrode and the lithium iron phosphate is excellent in performance, the first week efficiency is up to 96.96%, the mass of the lithium iron phosphate is taken as the mass of an active substance, the first week discharging specific capacity is up to 156.7mAh/g, and the energy density of the full battery is up to 328.27 Wh/kg.
Example 3
3ml of 0.001mol/L propyl amyl ether solution of anthracene lithium is taken to react with an artificial graphite electrode (the loading is about 2.5mg and the graphite content is 95 wt%) for 48 hours under the protection of inert atmosphere. After the reaction is completed, washing the reaction product for three times by using tetrahydrofuran, and drying the reaction product for later use.
Respectively using artificial graphite electrodes before and after pre-lithiation as positive electrodes and lithium metal as negative electrodes, and using ternary electrolyte (1M LiPF)6EC/DEC/DMC (v: v: v ═ 1:1:1)) half cells were assembled and subjected to charge and discharge tests. After pre-lithiation, the open-circuit voltage of the half-cell is reduced from 3.13V to 0.27V, and the first-cycle efficiency is improved from 85.03% to 99.31%.
Example 4
Taking 3ml of 10mol/L tetrahydrofuran solution of lithium phenanthrene to react with an artificial graphite electrode (the loading is about 2.5mg and the graphite content is 95 wt%) for 1s under the protection of inert atmosphere. After the reaction is completed, washing the mixture for three times by using methyl propyl ether, and drying the mixture for later use.
Respectively using artificial graphite electrodes before and after pre-lithiation as positive electrodes and lithium metal as negative electrodes, and using ternary electrolyte (1M LiPF)6EC/DEC/DMC (v: v: v ═ 1:1:1)) half cells were assembled and subjected to charge and discharge tests. After prelithiation, the open circuit voltage of the half cell was reduced from 3.07V to 0.22V, and the first cycle efficiency was improved from 84.96% to 98.71%.
Example 5
3ml of 0.05mol/L pyrene lithium ethyl tetrahydrofuran solution is taken to react with an artificial graphite electrode (the loading is about 2.5mg and the graphite content is 95 wt%) for 24 hours under the protection of inert atmosphere. Washing the mixture for three times by using propyl butyl ether after the reaction is completed, and drying the mixture for later use.
Respectively using artificial graphite electrodes before and after pre-lithiation as positive electrodes and lithium metal as negative electrodes, and using ternary electrolyte (1M LiPF)6EC/DEC/DMC (v: v: v ═ 1:1:1)) half cells were assembled and subjected to charge and discharge tests. After prelithiation, the open circuit voltage of the half cell was reduced from 3.13V to 0.28V, and the first cycle efficiency was improved from 84.86% to 98.91%.
Example 6
3ml of 5mol/L lithium perylene phenyl tetrahydrofuran solution is taken to react with an artificial graphite electrode (the loading is about 2.5mg and contains 95 wt% of graphite) for 10s under the protection of inert atmosphere. Washing the reaction product for three times by using ethyl butyl ether after the reaction is completed, and drying the reaction product for later use.
Respectively using artificial graphite electrodes before and after pre-lithiation as positive electrodes and lithium metal as negative electrodes, and using ternary electrolyte (1M LiPF)6EC/DEC/DMC (v: v: v ═ 1:1:1)) half cells were assembled and subjected to charge and discharge tests. After prelithiation, the open circuit voltage of the half cell decreased from 3.22V to 0.27V, and the first cycle efficiency increased from 84.73% to 98.86%.
In conclusion, the method for pre-lithiating the graphite negative electrode by using the monoether as the solvent and the radical anion as the lithiation reagent has the advantages of obvious effect, simplicity, convenience, easiness and high safety, and does not influence the electrochemical performance of the graphite material. After the graphite electrode pre-lithiated by the method is matched into a full cell, the full cell with high first-week efficiency and high energy density can be obtained, and the method has wide research prospect and application value.
The embodiments described above are only preferred examples of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (7)
1. The chemical prelithiation method for graphite electrode of lithium ion battery is characterized by comprising the following steps:
dissolving lithiation reagent containing anion free radical in monobasic ether to obtain lithiation reagent solution with concentration of 0.001-10 mol/L;
the prepared graphite negative plate of the lithium ion battery is contacted with a lithiation reagent solution for reaction for 1s-48h, and a pre-lithiated graphite electrode is obtained after washing and drying;
the monoether is one or a mixture of methyl tetrahydrofuran, dimethyl tetrahydrofuran, ethyl tetrahydrofuran, diethyl tetrahydrofuran and phenyl tetrahydrofuran;
the lithiation reagent containing the anion free radical is one or a mixture of naphthalene lithium, methylnaphthalene lithium, dimethylnaphthalene lithium, tetramethylnaphthalene lithium, anthracene lithium, methylanthracene lithium, dimethylanthracene lithium, tetramethylanthracene lithium, phenanthrene lithium, methylpheny lithium, dimethylphenanthrene lithium, trimethylphenanthrene lithium, tetramethylphenanthrene lithium, pyrene lithium, methylpyrene lithium, dimethylpyrene lithium, trimethylpyrene lithium, tetramethylpyrene lithium, perylene lithium, methylperylene lithium, dimethylperylene lithium, trimethylperylene lithium, tetramethylperylene lithium, biphenyl lithium, methylbiphenyl lithium, dimethylbiphenyl lithium and tetramethylbiphenyl lithium;
the washing solvent is one or mixture of methyl tetrahydrofuran, dimethyl tetrahydrofuran, ethyl tetrahydrofuran, diethyl tetrahydrofuran, phenyl tetrahydrofuran and carbonate.
2. The chemical prelithiation method for graphite electrode of lithium ion battery as claimed in claim 1, wherein said negative graphite plate is made from the following constituents (by weight portion): 70-99 parts of graphite negative electrode active material, 0.5-20 parts of conductive agent and 0.5-10 parts of binding agent.
3. The chemical prelithiation method for graphite electrodes of lithium ion batteries according to claim 2, wherein the graphite negative electrode active material is one or a mixture of natural graphite, artificial graphite, modified graphite, and a carbon material having a high degree of graphitization.
4. The chemical prelithiation method for graphite electrode of li-ion battery as claimed in claim 2, wherein said conductive agent is one or a mixture of acetylene black, ketjen black, Super P, MCMB, and carbon nanotubes.
5. The chemical prelithiation method for graphite electrode of Li-ion battery as claimed in claim 2, wherein said binder is one or a mixture of PVDF, CMC, PAA and SBR.
6. The chemical prelithiation method of graphite electrode for lithium ion battery according to claim 1, wherein the concentration of said lithiation reagent solution is 0.01-5 mol/L.
7. The chemical prelithiation method for graphite electrode of Li-ion battery as claimed in claim 1, characterized in that the contact reaction time is 10s-24 h.
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