CN111916728A - Electrochemical doping method of lithium-rich manganese-based positive electrode material and lithium-rich manganese-based positive electrode material doped with same - Google Patents
Electrochemical doping method of lithium-rich manganese-based positive electrode material and lithium-rich manganese-based positive electrode material doped with same Download PDFInfo
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- CN111916728A CN111916728A CN202010679781.7A CN202010679781A CN111916728A CN 111916728 A CN111916728 A CN 111916728A CN 202010679781 A CN202010679781 A CN 202010679781A CN 111916728 A CN111916728 A CN 111916728A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011572 manganese Substances 0.000 title claims abstract description 63
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 40
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 55
- -1 alkali metal salt Chemical class 0.000 claims abstract description 55
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 238000007599 discharging Methods 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 16
- 230000004913 activation Effects 0.000 claims abstract description 12
- 239000013543 active substance Substances 0.000 claims abstract description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 22
- 229910001416 lithium ion Inorganic materials 0.000 claims description 22
- 150000003949 imides Chemical class 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 159000000000 sodium salts Chemical group 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 3
- RWZRMQCJFKLBBM-UHFFFAOYSA-N B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[K+] Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[K+] RWZRMQCJFKLBBM-UHFFFAOYSA-N 0.000 claims description 3
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- VPOIXCYASUPXIC-UHFFFAOYSA-J tetrasodium oxalate Chemical compound C(C(=O)[O-])(=O)[O-].C(C(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+].[Na+] VPOIXCYASUPXIC-UHFFFAOYSA-J 0.000 claims description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 abstract description 8
- 230000005653 Brownian motion process Effects 0.000 abstract description 3
- 238000005537 brownian motion Methods 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 18
- 159000000002 lithium salts Chemical class 0.000 description 18
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910019398 NaPF6 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910005546 NiaCobMncO2 Inorganic materials 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical class OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- LWNCNSOPVUCKJL-UHFFFAOYSA-N [Mg].[P] Chemical compound [Mg].[P] LWNCNSOPVUCKJL-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- AEXDMFVPDVVSQJ-UHFFFAOYSA-N trifluoro(trifluoromethylsulfonyl)methane Chemical group FC(F)(F)S(=O)(=O)C(F)(F)F AEXDMFVPDVVSQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/0459—Electrochemical doping, intercalation, occlusion or alloying
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides an electrochemical doping method of a lithium-rich manganese-based positive electrode material, which comprises the following steps: s1) assembling a positive electrode with an active substance being a lithium-rich manganese-based positive electrode material, an electrolyte containing an alkali metal salt and a negative electrode to obtain a battery; s2), standing the battery at room temperature, performing first-circle charging activation, and then discharging at a rate of 0.01-0.05C. Compared with the prior art, the lithium-rich manganese-based anode material has the advantages that the alkali metal salt is added into the electrolyte, and due to concentration effect, Brownian motion and the like, the alkali metal enters the lithium-rich manganese-based anode material and is doped into the lithium layer in the discharging process, so that the voltage attenuation of the lithium-rich manganese-based anode material in the circulating process is relieved by utilizing the pillar effect of alkali metal ions with larger radius and the effect of inhibiting transition metal ions from entering tetrahedral gaps, and the rate capability of the material is improved; the method is an electrochemical doping method, and the doping effect can be adjusted by controlling the concentration of alkali metal salt, the temperature of the battery and the charging and discharging conditions.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrochemical doping method of a lithium-rich manganese-based positive electrode material and a doped lithium-rich manganese-based positive electrode material.
Background
Energy consumption has been increasing at an alarming rate due to the significant growth of the population and the increased standard of living in developing countries. The use of fossil fuels for energy production causes increased environmental pollution and global warming, and therefore, it is essential to produce energy using renewable energy and store the energy in an efficient manner. The lithium ion battery is an important energy storage device, and can effectively avoid energy waste and improve the utilization efficiency of energy. Since the invention of the lithium ion battery, the energy density of the lithium ion battery is rising, but in recent years, the development of the lithium ion battery faces a bottleneck because of the slow development of the anode material of the lithium ion battery.
The energy density of a lithium ion battery depends on the specific capacity and redox potential of its electrode material. Compared with the traditional layered anode material, the actual specific discharge capacity of the lithium-rich manganese-based anode material reaches 300mAh-1The discharge voltage is about 3.5V, and the lithium ion battery is the most competitive and potential power lithium ion battery cathode material at present. Although the lithium-rich manganese-based positive electrode material has the above advantages, there are many problems: the coulomb efficiency corresponding to the first charge-discharge process is low, the interface condition of the electrode and the electrolyte is unstable, the lithium ion diffusion coefficient is low, the multiplying power performance is not ideal enough, the voltage attenuation and the energy density are reduced in the circulation process, and the like.
Wherein, because partial transition metal of the lithium-rich manganese-based positive electrode material is transferred to tetrahedral gaps in the circulation process, the material structure is converted to spinel, and voltage attenuation is caused; and chemically inactive Mn is generated after the first-turn activation of the lithium-rich manganese-based positive electrode material4+Resulting in a decrease in the conductivity of the material; in addition, the poor dynamic performance of the material also leads to poor rate capability. Therefore, the voltage attenuation and the poor rate capability are two very critical factors that hinder the practical application of the lithium-rich manganese-based cathode material.
Doping and cladding are common technical means for modifying materials at present, and through doping some cations with larger radius and anions or cladding some materials of fast ion conductors, the voltage drop of the lithium-rich manganese-based anode material can be effectively inhibited and the rate capability of the lithium-rich manganese-based anode material can be improved. However, most of the existing techniques for preparing the lithium-rich manganese-based doped anode material are adopted in the process of preparing the lithium-rich manganese-based anode materialWhen element doping is carried out, a compound containing a doping element can generate certain influence on the structural growth of the lithium-rich manganese-based positive electrode material, for example, when doping is excessive, a prepared material can generate impurity phases, but when doping is trace, due to too small doping amount, a large amount of medicines are lost in the transfer and reaction processes, doping is not carried out, or the effect is not ideal. Such as: chinese patent with publication number CN104218235A discloses a double-doped lithium-rich solid solution anode composite material and a preparation method thereof, wherein hydroxide or carbonate precursor, lithium salt and M are mixedaMb(MaIs one or a combination of Na and K, MbF, N and P), drying, heating, cooling to obtain the double-doped lithium-rich solid solution anode composite material; a molybdenum-doped lithium-rich manganese-based positive electrode material is prepared by a sol-gel method in Chinese patent with publication number CN 107768664A; the Chinese patent with publication number CN107591534A prepares a phosphorus-magnesium ion synergistically doped modified lithium-rich manganese-based positive electrode material by a precursor grinding and calcining method.
Disclosure of Invention
In view of the above, the present invention provides an electrochemical doping method for a lithium-rich manganese-based positive electrode material, which is simple in doping method and can be doped in a small amount.
The invention provides an electrochemical doping method of a lithium-rich manganese-based positive electrode material, which comprises the following steps:
s1) assembling a positive electrode with an active substance being a lithium-rich manganese-based positive electrode material, an electrolyte containing an alkali metal salt and a negative electrode to obtain a battery; the alkali metal salt is sodium salt and/or potassium salt;
s2), standing the battery at room temperature, performing first-circle charging activation, and then discharging at a rate of 0.01-0.05C.
Preferably, the molar ratio of lithium ions in the lithium-rich manganese-based positive electrode material to alkali metals in the alkali metal salt is (100-1000): 1.
preferably, the anion of the alkali metal salt is selected from one or more of hexafluorophosphate, tetrafluoroborate, dioxalate borate, difluorinated oxalate borate, perchlorate and bistrifluoromethylsulfonyl imide.
Preferably, the alkali metal salt is selected from one or more of sodium hexafluorophosphate, potassium hexafluorophosphate, sodium dioxalate, potassium dioxalate borate, sodium perchlorate, potassium perchlorate, sodium bistrifluoromethylsulphonylimide and potassium bistrifluoromethylsulphonylimide.
Preferably, the concentration of the alkali metal salt in the electrolyte is 10-3～10-2mol/L。
Preferably, the standing time at room temperature is 10-15 h.
Preferably, the first circle of charge activation has a rate of 0.1 to 0.2C.
Preferably, the temperature of the battery during discharging is 40 ℃ to 50 ℃.
Preferably, the number of cycles of the charging, activating and discharging in the step S2) is 2-5 cycles.
The invention also provides a lithium-rich manganese-based doped anode material prepared by the electrochemical doping method.
The invention provides an electrochemical doping method of a lithium-rich manganese-based positive electrode material, which comprises the following steps: s1) assembling a positive electrode with an active substance being a lithium-rich manganese-based positive electrode material, an electrolyte containing an alkali metal salt and a negative electrode to obtain a battery; the alkali metal salt is sodium salt and/or potassium salt; s2), standing the battery at room temperature, performing first-circle charging activation, and then discharging at a rate of 0.01-0.05C. Compared with the prior art, the lithium-rich manganese-based anode material has the advantages that the alkali metal salt is added into the electrolyte, and due to concentration effect, Brownian motion and the like, the alkali metal enters the lithium-rich manganese-based anode material and is doped into the lithium layer in the discharging process, so that the voltage attenuation of the lithium-rich manganese-based anode material in the circulating process is relieved by utilizing the pillar effect of alkali metal ions with larger radius and the effect of inhibiting transition metal ions from entering tetrahedral gaps, and the rate capability of the material is improved; the method is an electrochemical doping method, simplifies the doping process, avoids the loss in the doping process by dissolving a dopant in the whole electrolyte, can adjust the doping effect by controlling the concentration of alkali metal salt, the temperature of a battery and the charging and discharging conditions, can directly observe the doping effect through an electrochemical curve, and improves the efficiency of a doping experiment.
Drawings
Fig. 1 is a diagram showing specific capacity test results of lithium ion batteries obtained in examples 1 to 4 of the present invention and comparative example 1 for different cycle times.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides an electrochemical doping method of a lithium-rich manganese-based positive electrode material, which comprises the following steps: s1) assembling a positive electrode with an active substance being a lithium-rich manganese-based positive electrode material, an electrolyte containing an alkali metal salt and a negative electrode to obtain a battery; the alkali metal salt is sodium salt and/or potassium salt; s2), standing the battery at room temperature, performing first-circle charging activation, and then discharging at a rate of 0.01-0.05C.
The invention utilizes the electrochemical process to realize the alkali metal ion Na during discharge+And/or K+The voltage attenuation of the lithium-rich manganese-based anode material in the circulation process is improved, and the rate capability of the lithium-rich manganese-based anode material is improved.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
In the present invention, the lithium-rich manganese-based positive electrode material is preferably Li1.2NiaCobMncO2Wherein 0 is<a<1, preferably 0<a<0.8, more preferably 0.05. ltoreq. a.ltoreq.0.6, still more preferably 0.1. ltoreq. a.ltoreq.0.3, most preferably a is 0.13; 0<b<0.5, preferably 0<b<0.8, more preferably 0.05. ltoreq. b.ltoreq.0.6, still more preferably 0.1. ltoreq. b.ltoreq.0.3, most preferably b is 0.13; 0.5<c<1, preferably 0.51. ltoreq. c.ltoreq.0.8, more preferably 0.54. ltoreq. c.ltoreq.0.6; the positive electrode with the active substance being the lithium-rich manganese-based positive electrode material preferably comprises a positive electrode current collector and a positive electrode current collector coated with the positive electrode current collectorA positive electrode paste on the body; the thickness of the positive electrode current collector is preferably 10-20 μm, more preferably 13-18 μm, and further preferably 15 μm; the positive electrode slurry preferably comprises a lithium-rich manganese-based positive electrode material, a conductive agent and a binder; the mass ratio of the lithium-rich manganese-based positive electrode material to the conductive agent to the binder is preferably (5-10): 1:1, more preferably (6-10): 1:1, and preferably (7-9): 1:1, most preferably 8:1: 1; the conductive agent is preferably carbon black; the binder is preferably polyvinylidene fluoride; the positive electrode slurry preferably uses N-methyl pyrrolidone as a solvent.
In the present invention, the electrolyte contains an alkali metal salt; the alkali metal salt is sodium salt and/or potassium salt; the anion of the alkali metal salt is preferably an anion capable of serving as an electrolyte of a lithium ion battery, and is more preferably one or more of hexafluorophosphate, tetrafluoroborate, dioxalate borate, difluorine oxalate borate, perchlorate and bis (trifluoromethyl) sulfonyl imide; the alkali metal salt is preferably one or more of sodium hexafluorophosphate, potassium hexafluorophosphate, sodium dioxalate, potassium dioxalate borate, sodium perchlorate, potassium perchlorate, sodium bistrifluoromethylsulfonyl imide and bistrifluoromethylsulfonyl imide potassium; the concentration of the alkali metal salt in the electrolyte is preferably 10-3～10-2mol/L; in some embodiments provided herein, the alkali metal salt concentration is preferably 1 × 10-3mol/L; in some embodiments provided herein, the alkali metal salt concentration is preferably 5 × 10-3mol/L; in some embodiments provided herein, the alkali metal salt concentration is preferably 1 × 10-2mol/L; the electrolyte preferably further comprises a carbonate solvent and a lithium salt; the carbonate solvent is preferably two or more of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC); the concentration of lithium salt in the electrolyte is preferably 1-1.2 mol/L; the lithium salt is preferably lithium hexafluorophosphate (LiPF)6) Lithium bis (oxalato) borate (LiBOB), lithium perchlorate (LiClO)4) And lithium bistrifluoromethylsulfonyl imide (LiTFSI).
The negative electrode is not particularly limited as long as it is a negative electrode of a lithium ion battery well known to those skilled in the art, and a metallic lithium negative electrode is preferable in the present invention.
Assembling a positive electrode with an active substance being a lithium-rich manganese-based positive electrode material, an electrolyte containing an alkali metal salt and a negative electrode to obtain a battery; the molar ratio of lithium ions to alkali metals in the alkali metal salt in the lithium-rich manganese-based positive electrode material is preferably (100-1000): 1; in some embodiments provided herein, the molar ratio of lithium ions to alkali metal in the alkali metal salt in the lithium-rich manganese-based positive electrode material is preferably 100: 1; in some embodiments provided herein, the molar ratio of lithium ions to alkali metal in the alkali metal salt in the lithium-rich manganese-based positive electrode material is preferably 100: 1; in some embodiments provided herein, the molar ratio of lithium ions in the lithium-rich manganese-based positive electrode material to alkali metal in the alkali metal salt is preferably 200: 1; in other embodiments provided herein, the molar ratio of lithium ions in the lithium-rich manganese-based positive electrode material to alkali metal in the alkali metal salt is preferably 1000: 1; the cell is preferably a button electrode.
Standing the battery at room temperature; the standing time is preferably 10-15 h, more preferably 10-14 h, still more preferably 11-13 h, and most preferably 12 h.
After standing, performing first-circle charging activation; the charge activation rate is preferably 0.1 to 0.2C, and more preferably 0.1C; the voltage for charging activation is preferably 2-4.6V.
After charging, preferably standing; the standing time is preferably 5-20 min, more preferably 5-15 min, still more preferably 8-12 min, and most preferably 10 min.
Then discharging at 0.01-0.05C multiplying power; the temperature of the battery during discharging is preferably 40-50 ℃, more preferably 42-48 ℃, and further preferably 45 ℃; the discharge rate is preferably 0.02C-0.05C, more preferably 0.04C-0.05C; because the alkali metal salt is dissociated into alkali metal ions and anion groups in the electrolyte, the alkali metal ions are surrounded by solvent molecules to form an ion-solvation pair, when the temperature is increased, the solvation effect of the ions is reduced, the viscosity of the electrolyte is reduced, the ion movement speed is accelerated, meanwhile, the discharge is carried out at a very small multiplying power, the polarization in the battery is reduced by the very small multiplying power, the resistance borne by the ions during the movement is reduced, the mobility of the ions is also increased, because the concentration of lithium salt in the electrolyte is far greater than that of the alkali metal salt, the conductivity of the electrolyte is firstly increased and then reduced along with the increase of the concentration of the lithium salt, when the concentration of the lithium salt is higher than 1.1mol/L, the discharge multiplying power is reduced (not lower than 0.01C), through the above process, the alkali metal ions are more easily attracted to the surface of the positive electrode material during the discharge, and the alkali metal ions gradually enter the lithium, doping into the lithium layer.
According to the invention, in order to improve the doping effect, cyclic charge-activated discharge is preferred; the cycle number of the charging, activating and discharging is preferably 2-5 circles, more preferably 3-5 circles, and further preferably 4-5 circles.
According to the invention, the alkali metal salt is added into the electrolyte, and due to concentration effect, Brownian motion and the like, the alkali metal enters the lithium-rich manganese-based anode material and is doped into the lithium layer in the discharging process, so that the voltage attenuation of the lithium-rich manganese-based anode material in the circulating process is relieved by utilizing the pillar effect of alkali metal ions with larger radius and the effect of inhibiting transition metal ions from entering tetrahedral gaps, and the multiplying power performance of the material is further improved; the method is an electrochemical doping method, simplifies the doping process, avoids the loss in the doping process by dissolving a dopant in the whole electrolyte, can adjust the doping effect by controlling the concentration of alkali metal salt, the temperature of a battery and the charging and discharging conditions, can directly observe the doping effect through an electrochemical curve, and improves the efficiency of a doping experiment.
The invention also provides a lithium-rich manganese-based doped positive electrode material prepared by the electrochemical doping method, which is preferably Li1.2-xMxNiaCobMncO2(ii) a Wherein (1.2-x): x is preferably (100-1000): 1; m is sodium and/or potassium.
In order to further illustrate the present invention, the following describes the electrochemical doping method of the lithium-rich manganese-based positive electrode material and the doped lithium-rich manganese-based positive electrode material in detail with reference to the following examples.
The reagents used in the following examples are all commercially available.
Example 1
In this example, an electrolyte was provided comprising 30% Ethylene Carbonate (EC) and 70% dimethyl carbonate (DMC) based on 100% total solvent volume, with 1.0% sodium hexafluorophosphate (NaPF) added based on 100% sum of the molar concentrations of lithium salt and alkali metal salt6)。
Uniformly mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC) serving as solvents according to the volume fraction of 3:7 in a glove box with the water content of less than 0.1ppm, and adding lithium salt LiPF6Preparing a solution with the total concentration of lithium salt and alkali metal being 1.0mol/L with sodium hexafluorophosphate, uniformly stirring to completely dissolve the lithium salt and the alkali metal, and removing water and impurities from the prepared electrolyte through a molecular sieve and activated carbon to obtain the purified electrolyte.
Selecting Li as lithium-rich manganese-based anode material1.2Ni0.13Co0.13Mn0.54O2Mixing conductive agent carbon black (SP) and binder (PVDF) according to the mass ratio of 8:1:1, adding NMP to prepare a mixture into slurry, uniformly stirring the slurry by a homogenizer, coating the slurry on an aluminum foil with the thickness of 15 mu m by a scraper machine, drying the aluminum foil by blowing at 80 ℃ for 4h, and drying the aluminum foil in vacuum at 120 ℃ for 4h to prepare a positive plate for the button cell (the total mass of active substances, the conductive agent and the binder on the positive plate is 8.88mg), and dropwise adding 0.1ml of the electrolyte into a glove box to finish Li1.2-xNaxNi0.13Co0.13Mn0.54O2And (3) assembling the lithium metal CR2032 button cell, standing for 12 hours at room temperature, charging and activating the cell for the first time at a rate of 0.1C in a voltage range of 2-4.6V, standing for 10min after charging is finished, raising the temperature of the cell to 45 ℃, discharging the cell at a rate of 0.05C, cycling for 5 cycles, performing charging and discharging cycles at rates of 0.2C, 0.5C, 1C and 2C for 5 cycles respectively, and performing charging and discharging cycles at a rate of 1C for 100 times in total.
Example 2
In contrast to example 1, 0.5% sodium hexafluorophosphate (NaPF) was added, based on 100% of the sum of the molar concentrations of the lithium salt and the alkali metal salt6) (ii) a The rest is the same as in example 1.
Example 3
In contrast to example 1, 0.1% sodium hexafluorophosphate (NaPF) was added, based on 100% of the sum of the molar concentrations of the lithium salt and the alkali metal salt6) (ii) a The rest is the same as in example 1.
Example 4
In contrast to example 1, 0.5% sodium hexafluorophosphate (NaPF) was added, based on 100% of the sum of the molar concentrations of the lithium salt and the alkali metal salt6) And the temperature of the battery is always at room temperature; the rest is the same as in example 1.
Comparative example 1
The electrolyte is provided with 30 percent of Ethylene Carbonate (EC) and 70 percent of dimethyl carbonate (DMC) based on 100 percent of the total volume of the solvent, and LiPF with 1.0mol/L concentration of lithium salt is selected6。
Uniformly mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC) serving as solvents according to the volume fraction of 3:7 in a glove box with the water content of less than 0.1ppm, and adding lithium salt LiPF6Preparing a solution with the concentration of lithium salt of 1.0mol/L, uniformly stirring to completely dissolve the lithium salt, and removing moisture and impurities from the prepared electrolyte through a molecular sieve and activated carbon to obtain a purified electrolyte solution.
Selecting Li as lithium-rich manganese-based anode material1.2Ni0.13Co0.13Mn0.54O2Mixing conductive agent carbon black (SP) and binder (PVDF) according to the mass ratio of 8:1:1, adding NMP to prepare a mixture into slurry, uniformly stirring the slurry by a homogenizer, coating the slurry on an aluminum foil by a scraper machine, drying the aluminum foil by blowing at 80 ℃ for 4h, and drying the aluminum foil in vacuum at 120 ℃ for 4h to prepare a positive plate for a button cell, and assembling Li in a glove box by using the electrolyte1.2Ni0.13Co0.13Mn0.54O2The lithium metal CR2032 button cell is kept stand for 12 hours at room temperature, is charged and activated for the first circle at a rate of 0.1C under a voltage range of 2-4.6V, is kept stand for 10min after charging is finished, is discharged at a rate of 0.05C after the temperature of the cell is increased to 45 ℃, is charged and discharged for 5 circles after circulation, is respectively charged and discharged for 5 circles under rates of 0.2C, 0.5C, 1C and 2C, and is then charged and discharged for 100 circles at a rate of 1C.
The results of the performance test data of the lithium ion batteries of examples 1 to 4 and comparative example 1 are shown in table 1 and fig. 1.
TABLE 1 test conditions and 100-cycle voltage decay results for lithium ion batteries
| Example one another | Alkali metal salt species and concentration ratio | Temperature of | 100 turns voltage attenuation (mV) |
| Comparative example 1 | / | 45℃ | 152 |
| Example 1 | 1％NaPF6 | 45℃ | 115 |
| Example 2 | 0.5％NaPF6 | 45℃ | 103 |
| Example 3 | 0.1％NaPF6 | 45℃ | 121 |
| Example 4 | 0.5％NaPF6 | At room temperature | 126 |
Claims (10)
1. An electrochemical doping method of a lithium-rich manganese-based positive electrode material is characterized by comprising the following steps:
s1) assembling a positive electrode with an active substance being a lithium-rich manganese-based positive electrode material, an electrolyte containing an alkali metal salt and a negative electrode to obtain a battery; the alkali metal salt is sodium salt and/or potassium salt;
s2), standing the battery at room temperature, performing first-circle charging activation, and then discharging at a rate of 0.01-0.05C.
2. The electrochemical doping method according to claim 1, wherein the molar ratio of lithium ions to alkali metals in the alkali metal salt in the lithium-rich manganese-based positive electrode material is (100-1000): 1.
3. the electrochemical doping method of claim 1, wherein the anion of the alkali metal salt is selected from one or more of hexafluorophosphate, tetrafluoroborate, dioxalate borate, difluorinated borate, perchlorate, and bistrifluoromethylsulfonyl imide.
4. The electrochemical doping method of claim 1, wherein the alkali metal salt is selected from one or more of sodium hexafluorophosphate, potassium hexafluorophosphate, sodium dioxalate, potassium dioxalate borate, sodium perchlorate, potassium perchlorate, sodium bistrifluoromethylsulfonyl imide and potassium bistrifluoromethylsulfonyl imide.
5. Electrochemical doping method according to claim 1, characterized in that in the electrolyte solutionAlkali metal salt concentration of 10-3～10-2mol/L。
6. The electrochemical doping method of claim 1, wherein the standing time at room temperature is 10-15 h.
7. The electrochemical doping method of claim 1, wherein the first-turn charging activation rate is 0.1C-0.2C.
8. The electrochemical doping method of claim 1, wherein the temperature of the cell at the time of discharging is 40 ℃ to 50 ℃.
9. The electrochemical doping method according to claim 1, wherein the number of cycles of the charge activation discharge in the step S2) is 2-5 cycles.
10. The doped lithium-rich manganese-based positive electrode material prepared by the electrochemical doping method according to any one of claims 1 to 9.
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