CN113991101A - Lithium supplementing method for lithium iron phosphate lithium ion battery and lithium iron phosphate lithium ion battery - Google Patents
Lithium supplementing method for lithium iron phosphate lithium ion battery and lithium iron phosphate lithium ion battery Download PDFInfo
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- CN113991101A CN113991101A CN202111238542.9A CN202111238542A CN113991101A CN 113991101 A CN113991101 A CN 113991101A CN 202111238542 A CN202111238542 A CN 202111238542A CN 113991101 A CN113991101 A CN 113991101A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 115
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 29
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 title claims abstract description 25
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 18
- 239000013589 supplement Substances 0.000 claims abstract description 37
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- 239000006258 conductive agent Substances 0.000 claims abstract description 24
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 239000013543 active substance Substances 0.000 claims abstract description 6
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000000654 additive Substances 0.000 claims description 21
- 230000000996 additive effect Effects 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- 239000011267 electrode slurry Substances 0.000 claims description 13
- 239000006230 acetylene black Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 8
- -1 carboxylate lithium modified acrylonitrile Chemical class 0.000 claims description 7
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- 238000000576 coating method Methods 0.000 claims description 6
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- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000006256 anode slurry Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000003273 ketjen black Substances 0.000 claims description 4
- 230000000670 limiting effect Effects 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 229940072056 alginate Drugs 0.000 claims description 2
- 235000010443 alginic acid Nutrition 0.000 claims description 2
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- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 239000002210 silicon-based material Substances 0.000 claims description 2
- 239000011366 tin-based material Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 238000007600 charging Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
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- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- 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 description 1
- 229910009055 Li1.2Ni0.2Mn0.6O2 Inorganic materials 0.000 description 1
- VFTKIWJJPDJBKD-UHFFFAOYSA-N OCCC[Na] Chemical group OCCC[Na] VFTKIWJJPDJBKD-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 230000036961 partial effect Effects 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000009469 supplementation Effects 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
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
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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
- H01M10/058—Construction or manufacture
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
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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
- H01M2004/028—Positive 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
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- 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 relates to a lithium supplementing method of a lithium iron phosphate lithium ion battery and the lithium iron phosphate lithium ion battery2MnO3·(1‑x)LiTMO2Wherein 0 is<x<TM is one or more of Ni, Co and Mn, the negative electrode material in the negative electrode plate comprises a negative electrode active substance, a conductive agent and a lithium-containing binder, and the positive electrode plate, the negative electrode plate and the diaphragm are assembled into a battery and then subjected to step current mixingThe battery is pre-charged in a constant-voltage current-limiting combination mode. The lithium supplementing method for the lithium iron phosphate lithium ion battery can supplement lithium for the positive electrode and the negative electrode at the same time, improves the overall first effect and the cycle performance of the battery, does not generate non-conductive residues, does not need additional special equipment, and is simple to operate and low in cost.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium supplementing method for a lithium iron phosphate lithium ion battery and the lithium iron phosphate lithium ion battery.
Background
The lithium iron phosphate battery has the characteristics of high safety, long service life, low cost and the like, and becomes a good idea of electrochemical energy storage. However, the power consumption cost of the energy storage system is still maintained at a higher level, and the economic model yield is not ideal, so that the investment heat of the industry is not high, and the industry development is not favorable. The cycle life of the battery monomer and the system is prolonged, and the method is the most direct and effective mode for reducing the full life cycle electricity cost of the energy storage system, so that the development of the lithium iron phosphate battery with the ultra-long cycle life has great significance.
There are many factors that affect the life of lithium ion batteries, and the number of lithium ions participating in energy transfer is continuously reduced. It should be noted that the total amount of lithium in the battery is not reduced, but the amount of "activated" lithium ions is reduced, and the "deactivated" lithium ions are trapped in a certain place or the active channels are blocked, and cannot freely participate in the cyclic charge and discharge process. The cycle of the current common lithium iron phosphate battery for energy storage is generally 4000-.
The method for supplementing lithium mainly comprises the steps of supplementing lithium to a positive electrode and supplementing lithium to a negative electrode, wherein the lithium supplementation to the positive electrode is mainly realized by adding a lithium-rich compound into a positive electrode active substance, and the lithium-rich compound is irreversibly decomposed during formation, so that lithium ions are released to participate in the formation of a negative electrode SEI film, and active lithium ions (8% -10%) which are lost for the first time during the formation of the traditional lithium ion battery are compensated. For example, patent CN108232343A discloses a lithium supplement additive for a lithium ion battery anode, which is added to provide an excessive lithium source during the first charging process of the anode, so as to compensate the consumption of lithium ions of SEI formed by the anode and the cathode, thereby improving the first coulombic efficiency and cycle performance of the battery. The positive electrode lithium supplement process has the advantages of simplicity, low process control environment requirement and safe production; the defects are that the irreversible decomposition residue of the lithium-rich compound is not conductive, and the addition amount limits the lithium supplement amount to be relatively limited, thereby inhibiting the popularization of the lithium supplement process of the anode.
The lithium supplement of the negative electrode is mainly realized by adding stabilized lithium powder (SLMP) into a negative electrode active material or coating lithium foil (5-10 mu m) on the surface of a negative electrode pole piece. After the battery is injected with liquid, the electrolyte and the lithium metal powder act to form an SEI film, so that active lithium ions lost for the first time when the traditional lithium ion battery is formed are compensated. The method has the advantages of sufficient lithium supplement amount, and has the main disadvantages of needing special lithium coating equipment, extremely strict requirements on environment, safety risks such as fire during production and the like.
Therefore, in order to solve the problems of lithium supplement of the positive electrode and lithium supplement of the negative electrode, a safe, efficient and economical method for supplementing lithium is urgently provided.
Disclosure of Invention
The invention aims to provide a lithium supplementing method of a lithium iron phosphate lithium ion battery and the lithium iron phosphate lithium ion battery, wherein the lithium supplementing method can be used for simultaneously supplementing lithium to a positive electrode and a negative electrode, the integral first effect and the cycle performance of the battery are improved, no non-conductive residue is generated, no extra special equipment is needed, the operation is simple, and the cost is low.
The technical scheme adopted by the invention for solving the problems is as follows: the lithium iron phosphate lithium ion battery is assembled by a positive plate, a negative plate and a diaphragm, wherein the positive plate contains an aluminum foil and a positive material coated on the surface of the aluminum foil, the positive material comprises lithium iron phosphate, a conductive agent, a binder and a lithium supplement additive, and the lithium supplement additive is a lithium-rich manganese material xLi2MnO3·(1-x)LiTMO2Wherein 0 is<x<1, TM is one or more of Ni, Co and Mn; the negative plate comprises a copper foil and a negative material coated on the surface of the copper foil, wherein the negative material comprises a negative active substance, a conductive agent and a lithium-containing binder.
Preferably, the lithium supplement additive accounts for less than or equal to 8wt% of the positive electrode material in percentage by mass.
More preferably, the lithium supplement additive accounts for 1-5 wt% of the positive electrode material.
More preferably, the lithium supplement additive accounts for 3.5-4.5 wt% of the positive electrode material.
Preferably, the lithium iron phosphate accounts for 80-95 wt% of the positive electrode material.
Preferably, the binder in the positive electrode material is one or more of fluorine-containing polyester, fiber type binder, polyacrylic resin, polyimide type binder and rubber type binder, and the mass percentage of the binder in the positive electrode material is less than or equal to 4 wt%.
More preferably, the binder accounts for 2.5-3.5 wt% of the positive electrode material.
Preferably, the conductive agent in the positive electrode material is one or more of conductive carbon black, acetylene black, graphene, ketjen black, carbon fiber and carbon nanotubes, and the conductive agent accounts for less than or equal to 10wt% of the positive electrode material in percentage by mass.
More preferably, the conductive agent accounts for 1-4 wt% of the positive electrode material.
Preferably, the lithium-containing binder is one or more of hydroxypropyl cellulose lithium, carboxymethyl cellulose lithium, lithium alginate, lithium polyacrylate, polyacrylate lithium, carboxylate lithium modified acrylonitrile and carboxylic acid lithium modified styrene butadiene rubber, and the lithium-containing binder accounts for less than or equal to 4wt% of the negative electrode material.
More preferably, when the lithium-containing binder is hydroxypropyl cellulose lithium, the lithium-containing binder accounts for 1.3-1.8 wt% of the negative electrode material; when the lithium-containing binder is other lithium-containing binders except for the hydroxypropyl cellulose lithium, the lithium-containing binder accounts for 1.5-2.0 wt% of the negative electrode material.
Preferably, the negative active material is one or more of graphite, a silicon-based material, amorphous carbon, a metal oxide and a tin-based material, and accounts for 90-95 wt% of the negative material.
Preferably, the conductive agent in the negative electrode material is one or more of conductive carbon black, acetylene black, graphene, ketjen black, carbon fiber and carbon nanotubes, and the conductive agent accounts for less than or equal to 10wt% of the positive electrode material in percentage by mass.
Preferably, the conductive agent accounts for 1-2 wt% of the positive electrode material by mass.
The invention also aims to provide a lithium supplementing method for the lithium iron phosphate lithium ion battery, which comprises the following steps:
(1) preparation of positive plate
Dissolving lithium iron phosphate, a conductive agent, a binder and a lithium supplement additive in a solvent according to a certain mass ratio, uniformly stirring to obtain anode slurry, coating the anode slurry on an aluminum foil, and rolling, slitting and die-cutting to obtain an anode sheet;
(2) preparation of negative plate
Dissolving a polar active substance, a conductive agent and a lithium-containing binder in deionized water according to a certain mass ratio, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on copper foil, and rolling, slitting and die-cutting to obtain a negative electrode sheet;
(3) assembling the positive plate, the negative plate and the diaphragm into a battery;
(4) after the lithium ion battery is assembled, working electrolyte is injected, and then the battery is pre-charged by adopting a mode of combining step current and constant voltage current limiting.
Preferably, the current in the step current is 0.02C-0.2C, and the voltage in the constant-voltage current limiting is 4.2V-4.5V.
Compared with the prior art, the invention has the advantages that:
1) the lithium iron phosphate positive pole piece adopts the lithium-rich manganese-based material as the lithium supplement additive to supplement lithium, and the lithium-rich manganese-based material contains LiTMO in the lithium-rich manganese-based material when the gram capacity of the lithium-rich manganese-based material is up to 250-300mAh/g and below 4.5V2Li in the lithium-rich manganese-based material when the lithium ion deintercalation is generated and is more than 4.5V2MnO3Lithium ion deintercalation occurs; the lithium-rich manganese-based material is oxidized by lattice oxygen in the first charge and discharge process, releases irreversible lithium ions to participate in negative electrode SEI formation so as to achieve the purpose of lithium supplement, and meanwhile, the voltage of the lithium-rich manganese-based material can be gradually reduced in the circulation process, and the layered result is gradually converted into the spinel result to slowly release the irreversible lithium ions to supplement lithiumActive lithium consumed by the negative electrode is charged, and the surface of the lithium-rich manganese-based material is always conductive in a lithium supplementing mode, so that non-conductive residues are avoided; in addition, the used lithium supplement additive can stably exist in the atmosphere, the preparation process is simple and reliable, the requirements on the field process and the environmental working condition are reduced, and the cost of the whole process is further reduced.
2) According to the negative electrode lithium supplement pole piece, lithium supplement is carried out without adopting stabilized lithium powder and lithium foil, lithium is directly supplemented through a lithium-containing binder, the operation is simple, extra special equipment is not needed, and no safety risk exists; the lithium ion battery is used together with the anode lithium supplement, so that the defects of limited anode lithium supplement amount and the like are effectively overcome.
3) The lithium is supplemented by mixing the anode and the cathode, so that the overall first effect of the battery is improved, the active lithium lost in the circulation process of the battery can be supplemented in time, and the circulation performance of the battery is improved to a limited extent.
4) During formation, the voltage is controlled to be 4.2V-4.5V, the normal working voltage of the battery is controlled to be 2.5V-3.65V, and partial lithium stays at the negative electrode end, so that the potential of the negative electrode is reduced, and the over-discharge capacity of the negative electrode is improved; on the other hand, the maximum voltage of the lithium-rich manganese material at the positive terminal can bear 4.8V, and the overcharge capacity of the battery is greatly improved.
Drawings
FIG. 1 is a graph showing the charge/discharge capacity retention ratio in cycles and the cycle temperature in comparison with those of comparative example 1 and examples 1 to 3 in accordance with the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Examples
A lithium supplementing method for a lithium iron phosphate lithium ion battery comprises the following steps:
(1) preparation of positive plate
The positive electrode active material lithium iron phosphate (LFP), the lithium supplement additive (PA), the binder polyvinylidene fluoride (PVDF, Arkema HSV 900) and the conductive agent acetylene black (AC) are dissolved in N-methyl pyrrolidone (NMP) according to the mass ratio of the positive electrode formula in the table 1 and are uniformly stirred to obtain positive electrode slurry, the positive electrode slurry is coated on an aluminum foil, and the positive electrode sheet is obtained after rolling, slitting and die cutting.
(2) Preparation of negative plate
The negative electrode active material is graphite (C), the binder is hydroxypropyl cellulose lithium (HPMCLi) and lithium carboxylate modified styrene butadiene rubber, and the conductive agent is acetylene black (AC), the negative electrode active material and the conductive agent are dissolved in deionized water according to the mass ratio of the negative electrode formula in the table 1 and uniformly stirred to obtain negative electrode slurry, the negative electrode slurry is coated on copper foil, and the negative electrode sheet is obtained after rolling, slitting and die cutting.
(3) And assembling the positive plate, the negative plate and the diaphragm into the battery.
(4) After the lithium ion battery is assembled, working electrolyte (containing 1M lithium hexafluorophosphate, the solvent is a mixed solvent of diethyl carbonate, dimethyl carbonate and ethylene carbonate with the volume ratio of 2: 5) is injected, and then the battery is pre-charged by adopting a combination mode of step current and constant voltage current limiting, wherein the method specifically comprises the following steps: a) 0.05C to 3.0V; b) charging for 3h at 0.1 ℃; c) charging to 4.4V at 0.2C, and maintaining constant voltage charging to 0.05C.
Comparative example 1
A lithium supplementing method for a lithium iron phosphate lithium ion battery comprises the following steps:
(1) preparation of positive plate
Lithium iron phosphate (LFP) as a positive electrode active material, polyvinylidene fluoride (PVDF) as a binder and acetylene black (AC) as a conductive agent are dissolved in N-methyl pyrrolidone (NMP) according to the weight ratio of a positive electrode formula in the table 1 and stirred to obtain positive electrode slurry, the positive electrode slurry is coated on an aluminum foil, and a positive electrode sheet is obtained after rolling, slitting and die cutting.
(2) Preparation of negative plate
The negative electrode active material is graphite (C), the binder is hydroxypropyl cellulose sodium (HPMC) and Styrene Butadiene Rubber (SBR), and the conductive agent is acetylene black (AC), the negative electrode active material is dissolved in deionized water according to the mass ratio of the negative electrode formula in the table 1 and is uniformly stirred to obtain negative electrode slurry, the negative electrode slurry is coated on copper foil, and the negative electrode sheet is obtained after rolling, slitting and die cutting.
(3) And assembling the positive plate, the negative plate and the diaphragm into the battery.
(4) After the lithium ion battery is assembled, working electrolyte (containing 1M lithium hexafluorophosphate, wherein the solvent is a mixed solvent of diethyl carbonate, dimethyl carbonate and ethylene carbonate with the volume ratio of 2: 5) is injected, and then the battery is pre-charged in a constant current mode, wherein the method specifically comprises the following steps: charging at 0.05 deg.C for 15 min; 0.15C charge for 2 h.
Comparative example 2
The only difference from example 1 is: the method for pre-charging the battery by adopting a constant current mode specifically comprises the following steps: charging at 0.05 deg.C for 15 min; 0.15C charge for 2 h.
Comparative example 3
The only difference from example 1 is: the binder in the preparation of the negative plate is hydroxypropyl sodium cellulose (HPMC) and Styrene Butadiene Rubber (SBR).
Comparative example 4
The only difference from example 1 is: the lithium supplement additive is not added in the preparation of the positive plate.
Comparative example 5
The difference from example 1 is that: the lithium supplement additive adopts Li in CN108232343A6MnO4。
In the comparative examples and examples, except for the addition of the lithium supplement additive to the positive electrode slurry, other characteristics of the positive and negative electrode sheets, such as the area density, compaction, die cutting and slitting dimensions, were consistent, the effective areas of the positive and negative electrode sheets were the same, and the amount of electrolyte contained in the battery was kept consistent.
Description of the test methods: calculating the rated capacity of the battery, and performing a first constant current charge and discharge test on the battery at a current of 50A, wherein the voltage range is 2.5-3.65V; the battery was subjected to a cyclic charge and discharge test at a current of 120A.
Coulombic efficiency = (first discharge capacity/first charge capacity) × 100%
Capacity retention rate = (discharge capacity after cycle/first discharge capacity) 100%
TABLE 1
Note: wherein PA-1 is Li1.15Ni0.15Co0.5Mn0.6O2PA-2 is Li1.2Ni0.2Mn0.6O2
As shown in FIG. 1, FIG. 1 is a graph comparing the cycle charge/discharge capacity retention ratio and the cycle temperature of comparative example 1 and examples 1 to 3.
As can be seen from table 1 and fig. 1, the lithium supplement additive of the present invention can effectively compensate for lithium loss during battery cycling, and significantly improve the cycle life of the battery, wherein the lithium supplement additive PA-1 of the present invention has the most significant effect when accounting for 3.76wt%, and when the lithium supplement additive is more, the content of the active material of the conventional lithium iron phosphate positive electrode is reduced, which has a negative effect on the capacity of the battery and affects the energy density of the battery. The lithium supplement effect of the lithium supplement additive PA-2 is better than that of PA-1, the PA-2 contains rich nickel, the theoretical specific capacity is slightly higher than that of PA-1, and the later cycle performance PA-2 is obviously better than that of PA-1.
In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.
Claims (10)
1. The utility model provides a lithium iron phosphate lithium ion battery, is formed by positive plate, negative pole piece, unfamiliar equipment, its characterized in that: the positive plate comprises an aluminum foil and a positive material coated on the surface of the aluminum foil, wherein the positive material comprises lithium iron phosphate, a conductive agent, a binder and a lithium supplement additive, and the lithium supplement additive is a lithium-rich manganese material xLi2MnO3·(1-x)LiTMO2Wherein 0 is<x<1, TM is one or more of Ni, Co and Mn;
the negative plate comprises a copper foil and a negative material coated on the surface of the copper foil, wherein the negative material comprises a negative active substance, a conductive agent and a lithium-containing binder.
2. The lithium iron phosphate lithium ion battery of claim 1, wherein: the lithium supplement additive accounts for less than or equal to 8wt% of the mass percent of the positive electrode material.
3. The lithium iron phosphate lithium ion battery of claim 1, wherein: the lithium iron phosphate accounts for 80-95 wt% of the positive electrode material.
4. The lithium iron phosphate lithium ion battery of claim 1, wherein: the binder in the positive electrode material is one or more of fluorine-containing polyester, fiber type binder, polyacrylic resin, polyimide type binder and rubber type binder, and the mass percentage of the binder in the positive electrode material is less than or equal to 4 wt%.
5. The lithium iron phosphate lithium ion battery of claim 1, wherein: the conductive agent in the positive electrode material is one or more of conductive carbon black, acetylene black, graphene, ketjen black, carbon fiber and carbon nano tube, and the conductive agent accounts for less than or equal to 10wt% of the positive electrode material in percentage by mass.
6. The lithium iron phosphate lithium ion battery of claim 1, wherein: the lithium-containing binder is one or more of hydroxypropyl cellulose lithium, carboxymethyl cellulose lithium, lithium alginate, lithium polyacrylate, polyacrylate lithium, carboxylate lithium modified acrylonitrile and carboxylic acid lithium modified styrene butadiene rubber, and accounts for less than or equal to 4wt% of the negative electrode material.
7. The lithium iron phosphate lithium ion battery of claim 1, wherein: the negative electrode active material is one or more of graphite, a silicon-based material, amorphous carbon, a metal oxide and a tin-based material, and accounts for 90-95 wt% of the negative electrode material.
8. The lithium iron phosphate lithium ion battery of claim 1, wherein: the conductive agent in the negative electrode material is one or more of conductive carbon black, acetylene black, graphene, ketjen black, carbon fiber and carbon nano tube, and the conductive agent accounts for less than or equal to 10wt% of the positive electrode material in percentage by mass.
9. A lithium supplementing method for a lithium iron phosphate lithium ion battery is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of positive plate
Dissolving lithium iron phosphate, a conductive agent, a binder and a lithium supplement additive in a solvent according to a certain mass ratio, uniformly stirring to obtain anode slurry, coating the anode slurry on an aluminum foil, and rolling, slitting and die-cutting to obtain an anode sheet;
(2) preparation of negative plate
Dissolving a polar active substance, a conductive agent and a lithium-containing binder in deionized water according to a certain mass ratio, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on copper foil, and rolling, slitting and die-cutting to obtain a negative electrode sheet;
(3) assembling the positive plate, the negative plate and the diaphragm into a battery;
(4) after the lithium ion battery is assembled, working electrolyte is injected, and then the battery is pre-charged by adopting a mode of combining step current and constant voltage current limiting.
10. The lithium iron phosphate lithium ion battery lithium supplementing method according to claim 9, characterized in that: the current in the step current is 0.02C-0.2C, and the voltage in the constant-voltage current-limiting is 4.2V-4.5V.
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| CN113381001A (en) * | 2021-03-29 | 2021-09-10 | 万向一二三股份公司 | Lithium roll film for supplementing lithium to negative plate and application |
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