CN111048833B - High-voltage electrolyte and high-voltage lithium ion power battery - Google Patents
High-voltage electrolyte and high-voltage lithium ion power battery Download PDFInfo
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- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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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
Abstract
The invention discloses a high-voltage electrolyte, which comprises an electrolyte solvent, lithium salt and an electrolyte additive, wherein the electrolyte additive comprises fluoroethylene carbonate, ethylene sulfate, propylene sulfite, trifluoromethylphenylsulfide, allyloxytrimethylsilane and tris (trimethylsilane) borate, the electrolyte is suitable for a high-voltage lithium ion battery, the stability of an electrolyte system is strong in a high-voltage state, and the cycle life and the comprehensive performance of the battery can be effectively improved. The invention also discloses a high-voltage lithium ion power battery, which comprises a positive plate, a negative plate, a diaphragm and the high-voltage electrolyte, wherein the high-voltage electrolyte is matched with the improved positive high-nickel single crystal ternary material and the negative high-temperature graphitized artificial graphite, so that the mechanical strength and the electrochemical stability of the electrode are improved, the charge cut-off voltage is improved, the battery capacity and the battery endurance are high, and the battery cycle life is long.
Description
Technical Field
The invention relates to the technical field of lithium ion secondary batteries, in particular to a high-voltage electrolyte and a high-voltage lithium ion power battery.
Background
18650 is a lithium ion battery, has the advantages of light weight, large capacity, no memory effect, etc., its capacity is generally 1200-3600 mah, the cycle life can reach more than 500 times in normal use, and is more than twice of that of a common battery, and has high safety, no explosion, no combustion, no toxicity, and no pollution. In recent years, with the continuous development of new energy industries, the application field of lithium ion batteries is wider and wider. Therefore, the consumer market puts higher demands on the battery capacity, service life, endurance and the like of the lithium ion battery. At present, the main stream of the charging and discharging voltage of a lithium ion battery is 4.2V-2.75V, if the charging cut-off voltage is increased from 4.2V to 4.35/4.40V, the battery capacity is increased by 8-13%, and the endurance capacity of the battery is obviously improved, which is a new trend of the development of the lithium battery, but how to have high capacity, high voltage and long cycle is still a difficult problem of the lithium ion battery product.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the high-voltage electrolyte which is added with various electrolyte additives, is suitable for a high-voltage state, has strong stability and can effectively improve the cycle life and the comprehensive performance of the battery.
The invention also aims to provide a high-voltage lithium ion power battery applying the electrolyte, which improves the mechanical strength and electrochemical stability of an electrode, improves the charge cut-off voltage, and has high battery capacity and battery endurance and long battery cycle life by improving the battery formula and the pole piece structure.
One of the purposes of the invention is realized by adopting the following technical scheme:
a high voltage electrolyte comprising an electrolyte solvent, a lithium salt and an electrolyte additive, the electrolyte additive comprising the following components in weight percent: 2 to 4 percent of fluoroethylene carbonate, 0.4 to 0.6 percent of ethylene sulfate, 0.15 to 0.25 percent of propylene sulfite, 0.1 to 0.8 percent of trifluoromethylphenyl sulfide, 0.01 to 1.0 percent of allyloxytrimethyl silane and 0.05 to 1.0 percent of tris (trimethylsilane) borate.
Preferably, the electrolyte additive comprises the following components in percentage by weight: 3% of fluoroethylene carbonate, 0.5% of vinyl sulfate, 0.2% of propylene sulfite, 0.5% of trifluoromethylphenyl sulfide, 0.2% of allyloxytrimethylsilane and 0.4% of tris (trimethylsilane) borate.
Further, the electrolyte solvent comprises the following components in percentage by weight: 5-20% of ethylene carbonate, 5-20% of dimethyl carbonate and 60-90% of methyl ethyl carbonate.
Further, the concentration of the lithium salt is 1.2-1.5 mol/L.
Preferably, the concentration of the lithium salt is 1.4 mol/L.
The lithium ion battery completes the charging/discharging process by the back-and-forth movement of the lithium ions in the battery between the positive electrode and the negative electrode. In the first charging process of the battery, an electrolyte solvent reacts on the surface of negative graphite to form a negative SEI film, lithium ions are consumed in the process, and the reaction is irreversible. Therefore, the lithium ion battery increases reversible lithium ions in the battery and is beneficial to prolonging the service life of the battery by matching with other electrolyte components and preferably adopting the lithium salt concentration of 1.4 mol/L.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a high voltage lithium ion power battery comprising a positive electrode sheet, a negative electrode sheet, a separator and the high voltage electrolyte of any one of claims 1 to 3; the positive plate comprises a positive metal foil, a positive coating and a positive tab, and the negative plate comprises a negative metal foil, a negative coating and a negative tab.
Preferably, the positive electrode coating comprises a positive electrode active substance, a positive electrode conductive agent and a positive electrode binder, wherein the positive electrode active substance comprises a high-nickel single crystal ternary material LiNiXMnYCoZO2Wherein X is more than 0.80 and less than or equal to 0.95, Y is more than or equal to 0.01 and less than 0.1, Z is more than or equal to 0.01 and less than 0.1, and X + Y + Z is 1.0.
The negative electrode coating comprises a negative electrode active material, a negative electrode conductive agent, a negative electrode suspending agent and a negative electrode binder, wherein the negative electrode active material is artificial graphite, and the artificial graphite is prepared by graphitization at 3000-3300 ℃.
The positive lug is in conductive connection with the positive metal foil, and is positioned at 1/3-1/5 in the length direction of the positive plate; the negative electrode lug is in conductive connection with the negative metal foil, and the negative electrode lug comprises 2pcs negative electrode lugs which are arranged at two ends of the negative electrode piece respectively.
The positive metal foil is a metal aluminum foil or a carbon-coated aluminum foil; the negative metal foil is a metal copper foil or a carbon-coated copper foil.
Further, the tap density of the positive electrode active material is 1.8-2.2g/cm3(ii) a The specific surface area of the positive electrode active material is 0.4-0.42m2(ii)/g; d of the positive electrode active material50Is 3-7 μm; the gram capacity of the positive active material is 180-205 mAh/g.
The tap density of the negative active material is 1.0-1.2g/cm3(ii) a The specific surface area of the negative electrode active material is 0.8-1.2m2(ii)/g; d of the negative electrode active material50Is 13-17 μm; the gram capacity of the negative electrode active material is 340-360 mAh/g.
Further, the positive coating comprises the following components in percentage by weight: 93.0-97.2% of positive electrode active substance, 0.2-4.0% of positive electrode conductive agent and 1.0-4.0% of positive electrode binder; the negative electrode coating comprises the following components in percentage by weight: 94.0-96.8% of negative active material, 0.4-2.4% of negative conductive agent, 1.0-3.0% of negative suspending agent and 1.2-2.2% of negative binder.
Compared with the prior art, the invention has the beneficial effects that:
1. the high-voltage electrolyte disclosed by the invention is matched with lithium salt with the optimal concentration, an electrolyte solvent with the optimal proportion and various electrolyte additives, is suitable for a high-voltage lithium ion battery, improves the battery capacity, is strong in stability, is sufficient in reversible lithium ions, can effectively protect a positive electrode and a negative electrode during charging and discharging, and improves the cycle life and comprehensive performance of the battery under high voltage.
2. The improved positive plate has the advantages of smaller resistance, better conductivity, better cycle performance, safety and stability; the improved negative active material has stable internal structure and high lithium intercalation capability, is suitable for a high-voltage system, and is beneficial to improving the cycle life and the comprehensive performance of the battery.
3. The invention designs the positive electrode lug and the negative electrode lug with special structures, thereby reducing the internal resistance of the battery, improving the performance of the battery, reducing the heat generation quantity of the battery and improving the safety performance.
4. The high-voltage lithium ion power battery has the rated capacity of 2800mAh and the charge cut-off voltage of 4.35V/4.40V, improves the battery capacity, and has good battery performance, long service life, low cost of single raw material and high cost performance.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
The present embodiment provides a high voltage electrolyte including an electrolyte solvent, a lithium salt, and an electrolyte additive.
The electrolyte additive comprises the following components in percentage by weight: 2-4% of fluoroethylene carbonate (FEC), 0.4-0.6% of vinyl sulfate (DTD), 0.15-0.25% of Propylene Sulfite (PS), 0.1-0.8% of trifluoromethylphenyl sulfide (PTS), 0.01-1.0% of Allyloxytrimethylsilane (AMSL) and 0.05-1.0% of tris (trimethylsilane) borate (TMSB).
In the embodiment, a plurality of high-voltage electrolyte additives are added to synergistically improve the comprehensive performance of the battery. The FEC is a negative electrode film forming additive, and a compact SEI film with low impedance is formed on the surface of a negative electrode active material, so that the multiplying power, the circulation and the storage performance are improved; FEC can also continuously repair SEI film cracks caused by volume change of graphite particles in the later cycle period, and further cycle life is prolonged. The DTD is a negative electrode film forming additive, so that the first charge-discharge efficiency can be improved, and the initial capacity of the battery can be further improved; meanwhile, the occurrence of side reactions can be reduced, the gas generation in the battery is further reduced, and the cycle performance of the battery is favorably improved. The AMSL participates in film formation of the negative electrode, reduction reaction is carried out on the surface of the negative electrode before electrolyte solvent molecules are subjected to reduction reaction, so that negative electrode active substance particles are protected from being damaged by the solvent molecules, an SEI film with stable structure and performance is formed, and the rate performance of the battery is obviously improved; the temperature of the power battery is obviously increased in the high-rate discharge process, the electrolyte is decomposed at high temperature to generate H and F, and strong corrosive HF is formed in combination to corrode a current collector, so that the performance of the battery is reduced; the AMSL is used as a high-temperature stabilizing additive, and silicon-oxygen bonds and olefinic bonds of the AMSL are easy to capture decomposition products H and F of the electrolyte at high temperature, so that the current collector is prevented from being corroded, and the safety performance of the battery is improved. In addition, when the positive electrode is in a high-voltage state, the boron-containing additive TMSB is oxidized before the solvent to form a positive electrode protective film, so that the oxidative decomposition of the electrolyte is inhibited, and the cycle life of the battery is prolonged; the PS, the PTS and the TMSB have synergistic effect, an SEI film with stable structure, thin texture and small impedance is formed on the positive electrode, the occurrence of side reaction on the surface of the positive electrode is inhibited, the dissolution of metal ions of the positive electrode is inhibited, and the structural stability of the positive electrode under high voltage (high lithium removal degree) is protected.
The electrolyte solvent comprises the following components in parts by weight: 5-20% of Ethylene Carbonate (EC), 5-20% of dimethyl carbonate (DMC) and 60-90% of Ethyl Methyl Carbonate (EMC).
As a further preferable scheme, the electrolyte solvent comprises the following components in parts by weight: 10% of Ethylene Carbonate (EC), 10% of dimethyl carbonate (DMC) and 80% of Ethyl Methyl Carbonate (EMC).
Here, EC dielectric constant is high (about 29 times of DMC and EMC), and thus conductivity is high, facilitating lithium ion migration; but at the same time its viscosity is high (about 3 times DMC and EMC), which is detrimental to lithium ion transport. Therefore, the embodiment adopts a small amount of EC to improve the conductivity of the electrolyte, and simultaneously matches DMC and EMC solvents with low viscosity to reduce the viscosity of the electrolyte. In addition, the EMC melting point is low, about-55 ℃, the liquid is at normal temperature, and the temperature adaptability is strong; the EC melting point is about 36 ℃, the DMC melting point is about 4 ℃, the temperature adaptability is poor, the influence of the conductivity, viscosity and temperature adaptability of the high-voltage electrolyte is comprehensively considered, a specific electrolyte solvent formula is adopted, EMC is used as a main component, and EC and DMC are used as secondary components.
The lithium salt of the electrolyte of the embodiment is a high-concentration lithium salt, and the concentration is 1.4 mol/L. The reversible lithium ions in the battery are increased, and the lithium salt concentration is improved, so that the service life of the battery is prolonged.
As a further preferable scheme, the electrolyte additive comprises the following components in percentage by weight: 3% of fluoroethylene carbonate, 0.5% of vinyl sulfate, 0.2% of propylene sulfite, 0.5% of trifluoromethylphenyl sulfide (PTS), 0.2% of allyloxytrimethylsilane and 0.4% of tris (trimethylsilane) borate.
The embodiment also provides a lithium ion power battery using the high-voltage electrolyte, which comprises a positive plate, a negative plate, a diaphragm and the electrolyte; the battery positive plate comprises a positive metal foil, a positive coating intermittently coated on the positive metal foil and a 1pcs positive lug conductively connected with the positive metal foil; the battery negative plate comprises a negative metal foil, a negative coating intermittently coated on the negative metal foil, and a negative lug conductively connected with the negative metal foil.
The positive metal foil is a metal aluminum foil or a carbon-coated aluminum foil, and the negative metal foil is a metal copper foil or a carbon-coated copper foil.
The positive coating comprises the following components in percentage by weight:
93.0-97.2% of positive electrode active substance
0.2 to 4.0 percent of positive electrode conductive agent
1.0 to 4.0 percent of positive electrode binder
Wherein, the positive active substance adopts modified high-nickel single crystal ternary material LiNiXMnYCoZO2Wherein X is more than 0.80 and less than or equal to 0.95, Y is more than or equal to 0.01 and less than or equal to 0.1, Z is more than or equal to 0.01 and less than or equal to 0.1, and X + Y + Z is 1.0. The ternary material particles are mainly in a single crystal state, the single crystal form is regular, the surface appearance is smooth, the specific surface area of the particles is small, and the particle diameter D of the particles is50About 5. + -.3 μm. Compared with the conventional ternary material consisting of secondary particles, the single crystal particles have better conductivity and better cycle performance; because the crystal form of the single crystal particles is regular and the surface appearance is smooth, the single crystal particles are contacted with the conductive agent more tightly, the resistance of the prepared pole piece is smaller, and the cycle life of the battery is prolonged(ii) a The single crystal particles have small specific surface area, less side reaction in the formation charging process, less lithium ion consumption and less gas production compared with the conventional ternary method, so that a battery system can be better and more stable, and the comprehensive performance of the battery is better. The single crystal ternary material used in the embodiment is subjected to coating/doping modification, and has the advantages of stable structure, good safety and long cycle life.
Here, the tap density of the positive electrode active material is 1.8 to 2.2g/cm3The specific surface area is 0.4-0.42m2/g；D503-7 μm, and the gram volume is 180-205 mAh/g. By matching with the modified positive active material, the coating density and the roll compaction degree of the positive plate are also adjusted in the embodiment, so that the mechanical strength and the electrochemical stability of the positive electrode are improved.
The negative electrode coating comprises the following components in percentage by weight:
the negative electrode uses artificial graphite as an active material. The performance of graphite is improved by adjusting graphitization temperature and coating modification. In the process of manufacturing the graphite of the embodiment, the temperature in the graphitization process is increased to 3000-3300 ℃, so that carbon layers in the graphite become more regular and tend to be in a completely parallel state, the consistency of interlayer spacing is better, the stability of a microstructure of the material is improved, and the comprehensive performances of circulation, multiplying power, storage and the like are improved. Meanwhile, the lithium intercalation capability of the graphite is improved, and the graphite is suitable for a positive high-voltage system. Through coating modification, the graphite particles have smooth surfaces and good contact with electrolyte, and can form an SEI film with stable structure and consistent thickness with solvent molecules, thereby improving the comprehensive performance of the product.
Here, the tap density of the negative electrode active material is 1.0 to 1.2g/cm3The specific surface area is 0.8-1.2m2/g；D5013-17 μm, and the gram volume is 340-360 mAh/g. In this embodiment, the coating density and the roll compaction degree of the negative electrode sheet are adjusted by matching with the modified negative electrode active material, so as to improve the mechanical strength and the electrochemical stability of the negative electrode.
As a further preferred scheme, the position of the positive tab of the positive plate is 1/3-1/5 in the length direction of the positive plate, and the 2pcs negative tabs of the negative plate are respectively arranged at the two ends (the head and the tail) in the length direction of the negative plate, so that the internal resistance of the battery is reduced, the heat generation amount is reduced, the cycle performance of the battery is improved, and the safety performance is improved.
The embodiment also provides a preparation method of the high-voltage lithium ion power battery, which comprises the following steps:
preparing a positive plate: mixing the components of the positive coating with a solvent to prepare a positive coating, coating the positive coating on a positive metal foil, drying at the temperature of 100-;
preparing a negative plate: mixing the components of the negative coating to prepare a negative coating, coating the negative coating on a negative metal foil, drying at the temperature of 100 ℃ and 130 ℃, rolling, slitting and shearing the negative coating into a strip-shaped negative plate with the thickness of 175-;
assembling the battery: the polyethylene film diaphragm, the positive plate and the negative plate are superposed according to the sequence of 'diaphragm/negative plate/diaphragm/positive plate' and then wound into a cylindrical winding core, and an upper gasket and a lower gasket which play a role in protection are respectively sleeved at the two ends of the winding core; welding the negative electrode tab led out from the negative plate to the bottom of the battery steel shell by spot welding, and welding the positive electrode tab led out from the positive plate to the connecting plate of the battery cover plate by laser welding; after the battery core is fully baked, electrolyte is injected, the opening is sealed, the battery is placed for 48 hours, and the battery is chemically charged to 4.35V/4.40V, so that the high-voltage 18650-2800mAh lithium ion power battery is assembled.
As a further preferable scheme, the solid content of the positive electrode coating is 65-75%, and the solid content of the negative electrode coating is 45-55%.
The following describes the manufacturing method and test procedure of the lithium ion battery by three preferred embodiments:
example 1
Preparing a positive plate: the tap density is 2.0g/cm3Specific surface area 0.41m2/g，D505 mu m, and the gram capacity of 180-XMnYCoZO2Wherein X is 0.88, Y is 0.06 and Z is 0.06. Uniformly mixing 1.5 wt% of polyvinylidene fluoride, 2.0 wt% of positive electrode conductive agent and 96.5 wt% of positive electrode active substance with an N-methyl pyrrolidone solvent to prepare positive electrode slurry with the solid content of 69%; coating the positive electrode slurry on a metal aluminum foil with the thickness of 12 mu m in an intermittent manner, drying at the temperature of 100-130 ℃, rolling into a positive electrode sheet with the thickness of 139 mu m, cutting the positive electrode sheet into a strip shape, welding a positive electrode lug at the position of the gap foil of the positive electrode sheet, and cutting the positive electrode sheet to ensure that the position of the obtained positive electrode lug is 1/3-1/5 in the length direction of the positive electrode sheet.
Preparing a negative plate: the tap density is 1.1g/cm3Specific surface area 1.0m2/g，D5015 μm, and the gram capacity of 340-360 mAh/g. Adding 1.6 wt% of CMC (sodium carboxymethylcellulose) dry powder into deionized water, mixing to prepare a negative suspension agent glue solution with the solid content of 2.0%, adding 94.8 wt% of artificial graphite powder and 1.8 wt% of Super P (conductive carbon black) dry powder into the suspension agent glue solution, mixing, adding 1.8 wt% of SBR (styrene butadiene rubber) emulsion, mixing, adding a proper amount of deionized water, continuously mixing to prepare a negative slurry with the solid content of 50%, intermittently coating the negative slurry on a metal copper foil with the thickness of 8 mu m, drying at the temperature of 100 ℃ and 130 ℃, and rolling to prepare a negative plate with the thickness of about 179 mu m; cutting the obtained negative plate into a strip shape, welding 2pcs negative electrode lugs at the position of the negative plate gap foil, and cutting the negative plate to ensure that 1pcs negative electrode lugs are respectively arranged at the head end and the tail end of the negative plate in the length direction.
Assembling the battery: superposing a polyethylene film diaphragm with the thickness of 16 mu m with a positive plate and a negative plate according to the sequence of 'diaphragm/negative plate/diaphragm/positive plate' and then winding the superposed films into a cylindrical winding core, wherein the two ends of the winding core are respectively sleeved with an upper gasket and a lower gasket which play a role in protection; welding the negative electrode tab led out from the negative electrode piece to the bottom of the steel shell, and welding the positive electrode tab led out from the positive electrode piece to the cap aluminum sheet connecting piece by laser welding; after fully baking the battery cell, injecting the electrolyte and sealing; after the battery is placed in an environment with the temperature of 30-40 ℃ for 48h, a formation process is used for formation charging of the battery to 4.35V/4.40V, so that the high-voltage 18650-2800mAh lithium ion power battery is assembled.
Testing of the battery: constant-current constant-voltage charging (cutoff current is 0.01CA) is carried out on the battery by 0.2CA current until the voltage is 4.2V/4.35V/4.40V, and then the battery is discharged by 0.2CA constant current until the voltage is 2.75V, and the discharge capacity is the battery capacity; carrying out charge-discharge cycle life test on the battery by using a 0.5CA constant-current and constant-voltage charge and 1.0CA constant-current discharge system and a voltage range of 2.75-4.35V; the battery is subjected to charge-discharge cycle life test by a 0.5CA constant-current constant-voltage charge and 1.0CA constant-current discharge system with a voltage range of 2.75-4.40V.
Example 2
Preparing a positive plate: uniformly mixing 1.8 wt% of polyvinylidene fluoride, 1.6 wt% of positive electrode conductive agent, 96.6 wt% of active substance and N-methyl pyrrolidone solvent to prepare positive electrode slurry with 68% of solid; coating the positive electrode slurry on a metal aluminum foil with the thickness of 12 mu m in an intermittent manner, drying at the temperature of 100 ℃ and 130 ℃, rolling into a positive electrode sheet with the thickness of about 137 mu m, cutting the obtained positive electrode sheet into a strip shape, welding positive electrode lugs at the gap foil material of the positive electrode sheet, and cutting the positive electrode sheet to ensure that the positions of the positive electrode lugs are 1/3-1/5 in the length direction of the positive electrode sheet.
Preparing a negative plate: adding 1.5 percent by weight of CMC dry powder into deionized water for mixing to prepare a suspending agent glue solution with the solid content of 2.0 percent, adding 95.0 percent by weight of artificial graphite powder and 1.5 percent by weight of Super P dry powder into the suspending agent glue solution for mixing, then adding 2.0 percent by weight of SBR emulsion, adding a proper amount of deionized water for continuous mixing after mixing to prepare a negative electrode slurry with the solid content of 49 percent, intermittently coating the negative electrode slurry on a metal copper foil with the thickness of 8 mu m, drying at the temperature of 100 ℃ and 130 ℃, and rolling into a negative electrode sheet with the thickness of about 177 mu m; cutting the obtained negative plate into a strip shape, welding 2pcs negative electrode lugs at the position of the negative plate gap foil, and cutting the negative plate to ensure that 1pcs negative electrode lugs are respectively arranged at the head end and the tail end of the negative plate in the length direction.
Assembling the battery: the assembly is the same as in embodiment 1 and will not be described in detail.
Testing of the battery: the test method is the same as that of example 1, and is not described in detail here.
Example 3
Preparing a positive plate: uniformly mixing 1.3 wt% of polyvinylidene fluoride, 1.5 wt% of conductive agent, 97.2 wt% of active substance and N-methyl pyrrolidone solvent to prepare anode slurry with 70% of solid; coating the positive electrode slurry on a metal aluminum foil with the thickness of 12 mu m in an intermittent manner, drying at the temperature of 100-130 ℃, rolling into a positive electrode sheet with the thickness of about 136 mu m, cutting the obtained positive electrode sheet into a strip shape, welding positive electrode lugs at the gap foil of the positive electrode sheet, and cutting the positive electrode sheet to enable the positions of the positive electrode lugs to be 1/3-1/5 in the length direction of the positive electrode sheet.
Preparing a negative plate: adding 1.4 wt% of CMC dry powder into deionized water, mixing to prepare a suspending agent glue solution with the solid content of 2.0%, adding 95.8 wt% of artificial graphite powder and 1.4 wt% of Super P dry powder into the suspending agent glue solution, mixing, adding 1.4 wt% of SBR emulsion, mixing, adding a proper amount of deionized water, continuously mixing to prepare a negative electrode slurry with the solid content of 48%, intermittently coating the negative electrode slurry on a metal copper foil with the thickness of 8 microns, drying at the temperature of 130 ℃ of 100 ℃, and rolling to prepare a negative electrode sheet with the thickness of about 175 microns; cutting the obtained negative plate into a strip shape, welding 2pcs negative electrode lugs at the position of the negative plate gap foil, and cutting the negative plate to ensure that 1pcs negative electrode lugs are respectively arranged at the head end and the tail end of the negative plate in the length direction.
Assembling the battery: the assembly is the same as in embodiment 1 and will not be described in detail.
Testing of the battery: the test method is the same as that of example 1, and is not described in detail here.
Comparative example:
the battery was tested according to the test method of example 1 using a commercially available 4.35/4.40V 18650-2800mAh lithium ion power battery.
The test results are given in table 1 below:
table 1 performance of examples 1-3 prepared and comparative batteries
Table 1 shows the results of the battery tests in example 1, example 2, example 3 and comparative example. As can be seen from Table 1, the 4.35/4.40V battery capacities are all > 2800mAh, and as the charge cut-off voltage increases, the battery capacity increases; the voltage is increased from 4.20V to 4.35V, and the battery capacity is increased by about 9-11%; the voltage is increased from 4.2V to 4.40V, and the battery capacity is increased by about 11-13%; the capacity retention rate of the battery in the cycle test is more than or equal to 80 percent, the cycle life of 4.35V is prolonged to 1000 weeks from 400 weeks of the conventional battery in the market, and the cycle life of 4.40V is prolonged to 1000 weeks from 300 weeks of the conventional battery in the market. The embodiment of the invention solves the problem that the lithium ion battery product is difficult to have high capacity, high voltage and long cycle.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the scope of the present invention claimed in the present invention.
Claims (10)
1. The high-voltage electrolyte is characterized by comprising an electrolyte solvent, a lithium salt and an electrolyte additive, wherein the electrolyte additive comprises the following components in percentage by weight: 2 to 4 percent of fluoroethylene carbonate, 0.4 to 0.6 percent of ethylene sulfate, 0.15 to 0.25 percent of propylene sulfite, 0.1 to 0.8 percent of trifluoromethylphenyl sulfide, 0.01 to 1.0 percent of allyloxytrimethyl silane and 0.05 to 1.0 percent of tris (trimethylsilane) borate.
2. The high voltage electrolyte of claim 1, wherein the electrolyte additive comprises, in weight percent: 3% of fluoroethylene carbonate, 0.5% of vinyl sulfate, 0.2% of propylene sulfite, 0.5% of trifluoromethylphenyl sulfide, 0.2% of allyloxytrimethylsilane and 0.4% of tris (trimethylsilane) borate.
3. The high voltage electrolyte of claim 1, wherein the electrolyte solvent comprises, in weight percent: 5-20% of ethylene carbonate, 5-20% of dimethyl carbonate and 60-90% of methyl ethyl carbonate.
4. A high voltage lithium ion power battery comprising a positive electrode sheet, a negative electrode sheet, a separator and the high voltage electrolyte of any one of claims 1 to 3; the positive plate comprises a positive metal foil, a positive coating and a positive tab, and the negative plate comprises a negative metal foil, a negative coating and a negative tab.
5. The high voltage lithium ion power cell of claim 4, wherein the positive coating comprises a positive active material comprising a high nickel single crystal ternary material LiNi, a positive conductive agent, and a positive binderXMnYCoZO2Wherein X is more than 0.80 and less than or equal to 0.95, Y is more than or equal to 0.01 and less than 0.1, Z is more than or equal to 0.01 and less than 0.1, and X + Y + Z is 1.0.
6. The high voltage lithium ion power battery as claimed in claim 4, wherein the negative electrode coating comprises a negative electrode active material, a negative electrode conductive agent, a negative electrode suspending agent and a negative electrode binder, the negative electrode active material is artificial graphite prepared by graphitization at 3000-3300 ℃.
7. The high voltage lithium ion power cell of claim 4,
the positive lug is in conductive connection with the positive metal foil, and is positioned at 1/3-1/5 in the length direction of the positive plate; the negative electrode lug is in conductive connection with the negative metal foil, and the negative electrode lug comprises 2pcs negative electrode lugs which are arranged at two ends of the negative electrode piece respectively.
8. The high voltage lithium ion power battery of claim 4, wherein the positive metal foil is a metal aluminum foil or a carbon-coated aluminum foil; the negative metal foil is a metal copper foil or a carbon-coated copper foil.
9. The high voltage lithium ion power cell of claim 5, wherein the tap density of the positive active material is 1.8-2.2g/cm3(ii) a The specific surface area of the positive electrode active material is 0.4-0.42m2(ii)/g; d of the positive electrode active material50Is 3-7 μm; the gram capacity of the positive active material is 180-205 mAh/g.
10. The high voltage lithium ion power cell of claim 6, wherein the negative active material has a tap density of 1.0-1.2g/cm3(ii) a The specific surface area of the negative electrode active material is 0.8-1.2m2(ii)/g; d of the negative electrode active material50Is 13-17 μm; the gram capacity of the negative electrode active material is 340-360 mAh/g.
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| CN114221021A (en) * | 2021-12-10 | 2022-03-22 | 惠州亿纬锂能股份有限公司 | In-situ cured polymer electrolyte, preparation method thereof and lithium ion battery |
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