CN119581670A - A lithium ion battery - Google Patents
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- CN119581670A CN119581670A CN202411991369.3A CN202411991369A CN119581670A CN 119581670 A CN119581670 A CN 119581670A CN 202411991369 A CN202411991369 A CN 202411991369A CN 119581670 A CN119581670 A CN 119581670A
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Abstract
为克服现有锂离子电池在循环过程中出现气胀、阻抗增长等问题，本发明提供了一种锂离子电池，包括正极、负极以及非水电解液，所述负极包括负极活性材料，所述负极活性材料中含有硅基材料，所述硅基材料中的硅元素占负极活性材料的质量百分比为2%~50%；所述非水电解液包括添加剂，所述添加剂包括如结构式1所示的化合物中的至少一种：A‑D‑B‑E‑C结构式1其中，A、B、C各自独立地选自含有环状碳酸酯基、环状硫酸酯基、环状亚硫酸酯基、环状磺酸酯基、环状砜基、环状亚砜基、环状羧酸酯基或环状酸酐基的基团；D、E各自独立地选自单键、或含有亚烃基、醚键、硫氧双键或碳氧双键的基团；所述结构式1所示化合物的添加量为0.01~5.0%。本发明能够有效解决锂离子电池循环过程中气胀、阻抗增长等问题，具有优异的循环稳定性。In order to overcome the problems of bloating and impedance growth in the existing lithium ion batteries during the cycle process, the present invention provides a lithium ion battery, comprising a positive electrode, a negative electrode and a non-aqueous electrolyte, wherein the negative electrode comprises a negative electrode active material, the negative electrode active material comprises a silicon-based material, and the silicon element in the silicon-based material accounts for 2% to 50% by mass of the negative electrode active material; the non-aqueous electrolyte comprises an additive, and the additive comprises at least one of the compounds shown in structural formula 1: A-D-B-E-C Structural formula 1 wherein A, B, and C are each independently selected from a group containing a cyclic carbonate group, a cyclic sulfate group, a cyclic sulfite group, a cyclic sulfonate group, a cyclic sulfone group, a cyclic sulfoxide group, a cyclic carboxylate group or a cyclic anhydride group; D and E are each independently selected from a single bond, or a group containing an alkylene group, an ether bond, a sulfur-oxygen double bond or a carbon-oxygen double bond; the added amount of the compound shown in structural formula 1 is 0.01 to 5.0%. The present invention can effectively solve the problems of gas expansion, impedance growth and the like during the cycle of lithium-ion batteries and has excellent cycle stability.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a lithium ion battery.
Background
The lithium ion battery is widely applied to the fields of 3C digital equipment and new energy power automobiles due to the advantages of high energy density, long cycle life, small self-discharge rate, environmental protection and the like. In order to increase the energy density of lithium ion batteries, one of the directions is to use a negative active material with a high energy density. The silicon-based negative electrode material has a higher theoretical specific capacity (4200 mAh/g) and is far beyond the theoretical specific capacity (372 mAh/g) of the graphite negative electrode, so that the silicon-based negative electrode material becomes an important direction for improving the energy density of the lithium ion battery. However, the silicon-based negative electrode has a large volume effect (more than or equal to 300 percent) in the cycle process, so that the solid electrolyte interface film on the surface of the silicon-based negative electrode is continuously broken and regenerated in the battery cycle process, the consumption of electrolyte and the loss of active lithium are caused, and the interface impedance is increased, thereby deteriorating the cycle performance. Meanwhile, a great amount of reducing gas is generated due to side reaction in the charge and discharge process of the lithium ion battery, so that the battery is inflated, the cycle performance is rapidly deteriorated, the battery can be exploded when the gas in the battery is accumulated to a certain degree, and potential safety hazards can be brought.
It is therefore desirable to provide a lithium ion battery having a graphite and silicon-based composite material as a negative electrode, wherein the nonaqueous electrolyte is effective in improving the swelling and resistance increase of the lithium ion battery during the cycle, thereby improving the cycle performance of the battery.
Disclosure of Invention
The invention solves the technical problems of air inflation, impedance increase and the like in the circulation process of the traditional lithium ion battery, thereby providing the lithium ion battery with excellent circulation performance.
The aim of the invention is achieved by the following technical scheme:
the invention provides a lithium ion battery, which comprises an anode, a cathode and nonaqueous electrolyte, wherein the cathode comprises a cathode active material, the cathode active material contains a silicon-based material, and the silicon element in the silicon-based material accounts for 2-50% of the mass of the cathode active material;
The nonaqueous electrolytic solution includes a solvent, an electrolyte salt, and an additive including at least one of compounds represented by structural formula 1:
A-D-B-E-C
Structure 1
Wherein A, B, C are each independently selected from the group consisting of cyclic carbonate groups, cyclic sulfate groups, cyclic sulfite groups, cyclic sulfonate groups, cyclic sulfone groups, cyclic sulfoxide groups, cyclic carboxylate groups, or cyclic anhydride groups;
D. e are each independently selected from a single bond, or a group containing an alkylene group, an ether bond, a thioxy double bond, or a carbon-oxygen double bond;
The addition amount of the compound shown in the structural formula 1 is 0.01-5.0% based on 100% of the total mass of the nonaqueous electrolyte.
Optionally, A, B, C each independently contains a cyclic carbonate group, a cyclic sulfate group, a cyclic sulfite group, a cyclic sulfonate group, a cyclic sulfone group, a cyclic sulfoxide group, a cyclic carboxylic acid ester group, and a cyclic anhydride group in an amount of 1 to 5, and the total number of the cyclic carbonate group, the cyclic sulfate group, the cyclic sulfite group, the cyclic sulfonate group, the cyclic sulfone group, the cyclic sulfoxide group, the cyclic carboxylic acid ester group, and the cyclic anhydride group in A, B, C is 10 or less.
Alternatively, A, C are each independently selected from the group represented by structural formula 2:
Structure 2
Wherein n is an integer of 0 to 4, R 1 is selected from hydrogen, halogen, C1-C5 hydrocarbon group or halogenated hydrocarbon group, R 2、R3、R4、R5、R6、R7 is independently selected from C1-C3 alkylene group, C1-C3 alkoxy group, oxygen atom,、Or (b)At least one of R 2、R3、R4 is selected from、Or (b)And at least one of R 2、R3、R4 is selected from oxygen atoms, and at least one of R 5、R6、R7 is selected from、Or (b)And at least one of R 5、R6、R7 is selected from oxygen atoms.
Alternatively, B is selected from the group represented by structural formula 3:
Structure 3
Wherein m is an integer of 1 to 4, and R 8、R9、R10 is independently selected from C1 to C3 alkylene, C1 to C3 alkoxy, oxygen atom,、Or (b)At least one of R 8、R9、R10 is selected from、Or (b)And at least one of R 8、R9、R10 is selected from oxygen atoms.
Alternatively, D, E are each independently selected from the group represented by structural formula 4:
Structure 4
Wherein z is an integer of 0 to 4, R 11 and R 13 are each independently selected from a single bond or a C1 to C5 alkylene group, R 12 is a single bond,、、、、、、、、Or (b)。
Alternatively, D, E is each independently selected from a single bond or a C1 to C5 alkylene group, A, B, C is each independently selected from a substituted or unsubstituted cyclic carbonate group, cyclic sulfate group, cyclic sulfite group, cyclic sulfonate group, cyclic sulfone group, cyclic sulfoxide group, cyclic carboxylate group, or cyclic anhydride group;
Alternatively, A, B or C is substituted, the substituent is selected from halogen, hydrocarbyl or halocarbyl, more preferably A, B or C is substituted, the substituent is selected from halogen, alkyl or haloalkyl.
Alternatively, A and C are the same as each other, A and B are the same as each other or different from each other, and D and E are the same as each other.
Optionally, the compound shown in the structural formula 1 is selected from one or more of the following compounds:
optionally, the mass percentage of silicon element in the anode active material is T%, the mass percentage of the compound shown in the structural formula 1 in the nonaqueous electrolyte is W%, and the following matters are satisfied:
t is more than or equal to 2 and less than or equal to 10, W is more than or equal to 0.01 and less than or equal to 3; or 10< T.ltoreq.50, and 0.05.ltoreq.W.ltoreq.5.
Optionally, the silicon-based material is selected from at least one of a silicon material, an oxide of silicon, a silicon-carbon composite material, and a silicon alloy material.
According to the lithium ion battery provided by the invention, the silicon-based material is used as the negative electrode material, so that the lithium ion battery with high energy density can be prepared, on the basis of the silicon-based negative electrode material, the compound shown in the structural formula 1 is added into the electrolyte, so that the energy density can be improved, the problems of battery cycle gas expansion, impedance increase and the like can be remarkably improved, the generation of gas in the battery cycle process is reduced, the cycle capacity is obviously improved, and the inventor finds that the battery cycle performance is not improved linearly along with the increase of the content of the compound shown in the structural formula 1, the improvement of the battery performance by the compound shown in the structural formula 1 is related to the mass ratio of the silicon element to the negative electrode active material, and the cycle performance of the battery is remarkably improved when the mass ratio of the silicon element to the negative electrode active material is 2% -50% and the addition amount of the compound shown in the structural formula 1 is 0.01% -5.0%.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a lithium ion battery, which comprises an anode, a cathode and a nonaqueous electrolyte, wherein the cathode comprises a cathode active material, the cathode active material contains a silicon-based material, and the silicon element in the silicon-based material accounts for 2-50% of the mass of the cathode active material;
The nonaqueous electrolytic solution includes a solvent, an electrolyte salt, and an additive including at least one of compounds represented by structural formula 1:
A-D-B-E-C
Structure 1
Wherein A, B, C are each independently selected from the group consisting of cyclic carbonate groups, cyclic sulfate groups, cyclic sulfite groups, cyclic sulfonate groups, cyclic sulfone groups, cyclic sulfoxide groups, cyclic carboxylate groups, or cyclic anhydride groups;
D. e are each independently selected from a single bond, or a group containing an alkylene group, an ether bond, a thioxy double bond, or a carbon-oxygen double bond;
The addition amount of the compound shown in the structural formula 1 is 0.01-5.0% based on 100% of the total mass of the nonaqueous electrolyte.
According to the lithium ion battery provided by the invention, on the basis of a silicon-based anode material, by adding the compound shown in the structural formula 1 into a non-aqueous electrolyte, the lithium ion battery with high energy density can be prepared, meanwhile, the problems of battery cycle ballooning, impedance increase and the like can be remarkably improved, the generation of gas in the battery cycle process is reduced, the cycle capacity is obviously improved, but in other battery systems, the better improvement effect is difficult to achieve, and the inventor finds that the battery cycle performance is not improved linearly along with the increase of the content of the compound shown in the structural formula 1, the improvement of the battery performance by the compound shown in the structural formula 1 is related to the mass ratio of the silicon element to the anode active material, and the battery performance is remarkably improved when the mass ratio of the silicon element to the anode active material is 2% -50% and the addition amount of the compound shown in the structural formula 1 is 0.01% -5.0%.
Regarding the mutual relation between the compound shown in the structural formula 1 and silicon element in the anode active material, when the silicon content is 2% -50%, the compound shown in the structural formula 1 is applied to a silicon-based anode battery, in the battery formation process, the additive is subjected to reduction decomposition on the surface of the silicon-based anode to form an interfacial film, organic components in the interfacial film are complexed with the silicon element in a certain proportion, so that the volume effect of the silicon-containing anode in the charge-discharge process is effectively inhibited, the cyclic flatulence is improved, and the cyclic capacity is kept to be obviously improved. When the silicon content is more than 50%, the addition of the compound shown in the structural formula 1 cannot effectively improve the circulation, presumably because the addition of a small amount of the additive cannot form a complete complex and compact interface film in the formation process due to the excessively high silicon content, the protection of the silicon-based material is insufficient, the high-temperature cycle performance of the battery is basically not improved, and the addition of a large amount of the additive can cause the local excessive thickness of the interface film at the negative electrode interface, the impedance of the battery is seriously increased, the lithium removal and the non-uniformity are caused, and the cycle performance cannot be effectively improved.
In some embodiments, A, B, C each independently contains a cyclic carbonate group, cyclic sulfate group, cyclic sulfite group, cyclic sulfonate group, cyclic sulfone group, cyclic sulfoxide group, cyclic carboxylate group, or cyclic anhydride group in an amount of 1 to 5, and the total amount of cyclic carbonate groups, cyclic sulfate groups, cyclic sulfite groups, cyclic sulfonate groups, cyclic sulfone groups, cyclic sulfoxide groups, cyclic carboxylate groups, or cyclic anhydride groups of A, B, C is 10 or less.
In some embodiments A, C are each independently selected from the group represented by structural formula 2:
Structure 2
Wherein n is an integer of 0 to 4, R 1 is selected from hydrogen, halogen, C1-C5 hydrocarbon group or halogenated hydrocarbon group, R 2、R3、R4、R5、R6、R7 is independently selected from C1-C3 alkylene group, C1-C3 alkoxy group, oxygen atom,、Or (b)At least one of R 2、R3、R4 is selected from、Or (b)And at least one of R 2、R3、R4 is selected from oxygen atoms, and at least one of R 5、R6、R7 is selected from、Or (b)And at least one of R 5、R6、R7 is selected from oxygen atoms.
In a preferred embodiment, the combination of-R 3-R2-R4 -and-R 7-R5-R6 -are each independently selected from、、、、、Or (b)。
In some embodiments, B is selected from the group shown in structural formula 3:
Structure 3
Wherein m is an integer of 1 to 4, and R 8、R9、R10 is independently selected from C1 to C3 alkylene, C1 to C3 alkoxy, oxygen atom,、Or (b)At least one of R 8、R9、R10 is selected from、Or (b)And at least one of R 8、R9、R10 is selected from oxygen atoms.
In a preferred embodiment, the combined groups of-R 9-R8-R10 -are each independently selected from、、、、、Or (b)。
In some embodiments D, E are each independently selected from the group represented by structural formula 4:
Structure 4
Wherein z is an integer of 0 to 4, R 11 and R 13 are each independently selected from a single bond or a C1 to C5 alkylene group, R 12 is a single bond,、、、、、、、、Or (b)。
In some embodiments, a and C are the same as each other, a and B are the same as each other or different, and D and E are the same as each other.
In some embodiments D, E is each independently selected from a single bond or a C1 to C5 alkylene group, A, B, C is each independently selected from a substituted or unsubstituted cyclic carbonate group, cyclic sulfate group, cyclic sulfite group, cyclic sulfonate group, cyclic sulfone group, cyclic sulfoxide group, cyclic carboxylate group, or cyclic anhydride group, and A, B is each independently selected from a halogen, alkyl, or haloalkyl group when C is substituted.
By way of example, the compound of formula 1 may be selected from one or more of the following compounds:
In some embodiments D, E are each independently selected from the group represented by structural formula 4:
Structure 4
Wherein z is an integer from 1 to 4, R 11 and R 13 are each independently selected from a single bond or a C1 to C5 alkylene group, R 12 is selected from、、、、、、、、Or (b);
A. B, C are each independently selected from a substituted or unsubstituted cyclic carbonate group, cyclic sulfate group, cyclic sulfite group, cyclic sulfonate group, cyclic sulfone group, cyclic sulfoxide group, cyclic carboxylate group or cyclic anhydride group, preferably, A, B or C when substituted, the substituents are selected from halogen, hydrocarbyl or halogenated hydrocarbyl groups, more preferably A, B or C when substituted, the substituents are selected from halogen, alkyl or haloalkyl.
By way of example, the compound of formula 1 may be selected from one or more of the following compounds:
in some embodiments, the compound of formula 1 may also be selected from one or more of the following compounds:
The above is a part of the compounds claimed in the present invention, but is not limited thereto, and should not be construed as limiting the present invention.
The preparation method of the above-mentioned compound can be known to those skilled in the art based on common general knowledge in the field of chemical synthesis, knowing the structural formula of the compound represented by structural formula 1. For example:
compound 1-1 can be prepared by the following method:
placing sorbitol, dimethyl carbonate, a methanol alkaline substance catalyst potassium hydroxide, DMF and other organic solvents in a reaction vessel, reacting for a plurality of hours under the heating condition, adding a certain amount of oxalic acid to adjust the pH to be neutral, filtering, recrystallizing to obtain an intermediate product 1, esterifying the intermediate product 1, the carbonate, thionyl chloride and the like under the high temperature condition to obtain an intermediate product 2, and oxidizing the intermediate product 2 by using an oxidant such as sodium periodate and the like to obtain the compound 1-1.
Compounds 1-2 can be made by the following method:
The method comprises the steps of heating diacetone-D-mannitol, dimethyl carbonate, methanol, potassium carbonate, dioxane and the like, stirring for reacting for a plurality of hours, adding a certain amount of oxalic acid to adjust the pH value of a solution to be neutral, filtering, concentrating to obtain an intermediate product 3, adding a proper amount of pure water, carbonate, acid and the like into the intermediate product 3 to carry out hydrolysis reaction to obtain an intermediate product 4, preparing the intermediate product 4, thionyl chloride and carbonate solvent under the heating condition to obtain an intermediate product 5, and finally oxidizing the intermediate product 5 by using an oxidant such as sodium periodate and the like to obtain the compound 1-2.
In some embodiments, the compound of formula 1 is added in an amount of 0.01 to 5.0% based on 100% of the total mass of the nonaqueous electrolyte. Specifically, the compound represented by the structural formula 1 may be added in an amount of 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1.0%, 2.0%, 3.0%, 4.0%, 5.0%.
When the amount of the compound represented by the formula 1 is too small, the film formation protective effect is not achieved, and when the amount of the compound represented by the formula 1 is too large, the interface film formed at the negative electrode interface is too thick, which is unfavorable for lithium ion shuttling and the cycle performance is rather deteriorated, so that the cycle performance of the battery can be improved by adding an appropriate amount of the compound represented by the formula 1.
In some embodiments, the additive further comprises at least one of an unsaturated cyclic carbonate compound, a fluorinated cyclic carbonate compound, a sultone compound, lithium difluorophosphate, vinyl sulfate (DTD), lithium difluorosulfonimide (LiFSI);
In some embodiments, the unsaturated cyclic carbonate compound comprises at least one of Vinylene Carbonate (VC) and ethylene carbonate (VEC), the fluorinated cyclic carbonate compound comprises Fluorinated Ethylene Carbonate (FEC), and the sultone compound is at least one selected from 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS) and 1, 3-Propylene Sultone (PST).
In some embodiments, the total mass of the nonaqueous electrolyte of the lithium ion battery is 100%, the unsaturated cyclic carbonate compound content is 0.1-5%, the fluorinated cyclic carbonate compound content is 0.1-30%, the sulfonate lactone compound content is 0.1-5%, the lithium difluorophosphate content is 0.1-2%, the vinyl sulfate (DTD) content is 0.1-5%, and the bis (fluorosulfonyl) lithium imide (LiFSI) content is 0.1-5%.
In some embodiments, the solvent comprises one or more of an ether solvent, a nitrile solvent, a carbonate solvent, and a carboxylate solvent.
In some embodiments, the ethereal solvent includes a cyclic ether or a chain ether, the cyclic ether may be specifically but not limited to one or more of 1, 3-Dioxolane (DOL), 1, 4-Dioxane (DX), crown ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH 3 -THF), 2-trifluoromethyl tetrahydrofuran (2-CF 3 -THF), and the chain ether may be specifically but not limited to one or more of Dimethoxymethane (DMM), 1, 2-Dimethoxyethane (DME), diglyme (teggme). The nitrile solvent may be, but is not limited to, one or more of acetonitrile, glutaronitrile, malononitrile. The carbonate solvent comprises cyclic carbonate or chain carbonate, the cyclic carbonate can be one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), gamma-butyrolactone (GBL) and Butylene Carbonate (BC), and the chain carbonate can be one or more of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) and dipropyl carbonate (DPC). The carboxylate solvent may be, but is not limited to, specifically one or more of Methyl Acetate (MA), ethyl Acetate (EA), propyl acetate (EP), butyl acetate, propyl Propionate (PP), butyl propionate.
In some embodiments, the electrolyte salt comprises one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a zinc salt, and an aluminum salt.
In a preferred embodiment, the electrolyte salt is selected from lithium salts. In a more preferred embodiment, the lithium salt includes one or more of LiPF6、LiBF4、LiBOB、LiDFOB、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO2F)2.
In some embodiments, the concentration of the electrolyte salt in the nonaqueous electrolytic solution is 0.1mol/L to 8mol/L. In a preferred embodiment, the concentration of the electrolyte salt in the nonaqueous electrolytic solution is 0.5mol/L to 4mol/L. Specifically, the concentration of the electrolyte salt may be 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, or 4mol/L.
In some embodiments, the positive electrode includes a positive electrode active material capable of reversibly intercalating/deintercalating metal ions (lithium ions, sodium ions, potassium ions, magnesium ions, zinc ions, aluminum ions, etc.), preferably, the positive electrode active material is selected from at least one of nickel cobalt manganese ternary materials, nickel cobalt aluminum ternary materials, liFePO 4、LiCoO2、LiMnO2、LiNiMnO2, and composites thereof.
In some embodiments, the mass percentage of the silicon element in the anode active material is T, the mass percentage of the compound shown in the structural formula 1 in the nonaqueous electrolyte is w%, and the following matters are satisfied:
When T is more than or equal to 2 and less than or equal to 10, preferably, W is more than or equal to 0.01 and less than or equal to 3; or when 10< T.ltoreq.50, preferably 0.05.ltoreq.W.ltoreq.5.
According to the research and verification of the inventor, when the mass percentage of silicon element in the anode active material is between 2% and 10%, the addition of a proper amount of electrolyte containing 0.01% -3% of the compound shown in the structural formula 1 can effectively improve the high-temperature cycle performance of the battery, and when the addition amount is 3% -5%, the impedance is increased due to an interface film formed by the compound shown in the structural formula 1, and the cycle performance is reduced. When the mass percentage of silicon in the anode material is increased to 10% -50%, the optimal content of the compound shown in the structural formula 1 required for forming the complete interface film is increased, so that the cycle performance of the battery can be effectively improved when the content of the compound is 0.05% -5%.
In some embodiments, the silicon-based material is selected from at least one of a silicon material, an oxide of silicon, a silicon-carbon composite, and a silicon alloy material.
In some embodiments, a separator is also included in the battery, the separator being located between the positive electrode and the negative electrode.
The membrane can be an existing conventional membrane, and can be a ceramic membrane, a polymer membrane, a non-woven fabric, an organic-inorganic composite membrane and the like, including but not limited to a membrane such as single-layer PP (polypropylene), single-layer PE (polyethylene), double-layer PP/PE, double-layer PP/PP, and three-layer PP/PE/PP.
In some embodiments, the mass percentage of silicon element in the anode active material is 2% -50%. Specifically, the mass percentage of the silicon element in the anode active material may be 2%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%.
When the silicon content is 2% -50%, the compound shown in the structural formula 1 is applied to a silicon-based negative electrode battery, and in the battery formation process, the compound shown in the structural formula 1 is subjected to reduction decomposition on the surface of the silicon-based negative electrode to form an interface film. Organic components in the interface film are complexed with silicon element in a certain proportion, so that the volume effect of the silicon-containing anode in the charge-discharge process is effectively inhibited, the cyclic gas expansion is improved, and the cyclic capacity is kept obviously improved. When the silicon content is more than 50%, the addition of the compound represented by the structural formula 1 cannot effectively improve the cycle, presumably because the addition of a small amount of the compound represented by the structural formula 1 cannot form a complete complex and compact interfacial film in the formation process due to the excessively high silicon content, the protection of the silicon-based material is insufficient, the high-temperature cycle performance of the battery is basically not improved, and the addition of a large amount of the compound represented by the structural formula 1 can cause the local excessive thickness of the interfacial film at the negative electrode interface, the impedance of the battery is seriously increased and the deintercalation of lithium is uneven, and the cycle performance cannot be effectively improved.
The invention is further illustrated by the following examples.
1. Examples 1 to 62 and comparative examples 1 to 17
1) Preparation of electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and ethylmethyl carbonate (EMC) were mixed in mass ratio EC: DEC: emc=1:1:1, then lithium hexafluorophosphate (LiPF 6) was added to a molar concentration of 1mol/L, and then additives were added according to the respective tables. The additive is used in an amount that is a percentage of the total mass of the electrolyte.
2) Preparation of positive plate
The positive electrode active material LiNi 0.5Co0.2Mn0.3O2, conductive carbon black Super-P and binder polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 93:4:3, and then dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode slurry. The slurry is evenly coated on two sides of an aluminum foil, and the positive plate is obtained after drying, calendaring and vacuum drying, and an aluminum outgoing line is welded by an ultrasonic welder, and the thickness of the positive plate is 120-150 mu m.
3) Preparation of negative plate
The anode active material SiO-C (graphite: silicon=9:1), conductive carbon black Super-P, binder styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) were mixed in a mass ratio of 94:1:2.5:2.5, and then dispersed in deionized water to obtain an anode slurry. Coating the slurry on two sides of a copper foil, drying, calendaring and vacuum drying, and welding a nickel lead-out wire by an ultrasonic welder to obtain a negative plate, wherein the thickness of the negative plate is 120-150 mu m.
4) Preparation of the cell
And placing a three-layer isolating film with the thickness of 20 mu m between the positive plate and the negative plate, winding a sandwich structure formed by the positive plate, the negative plate and the diaphragm, flattening the winding body, putting into an aluminum foil packaging bag, and baking for 48 hours at the temperature of 75 ℃ in vacuum to obtain the battery cell to be injected with the liquid.
5) Injection and formation of battery cell
In a glove box with water and oxygen contents below 20ppm and 50ppm respectively, the prepared electrolyte is injected into a battery cell, and is subjected to vacuum packaging and is placed at 45 ℃ for 24 hours.
Then the first charge is conventionally formed by 0.05C constant current charging for 180min, 0.1C constant current charging for 180min,0.2C constant current charging for 120min, aging at 45 ℃ for 48h, secondary vacuum sealing, then further charging to 4.4V by 0.2C constant current, and discharging to 2.75V by 0.2C constant current.
Performance testing
1. The lithium ion batteries prepared in examples 1 to 62 and comparative examples 1 to 17 were subjected to the following performance tests, namely, high-temperature cycle performance test
The prepared lithium ion battery is placed in an oven with constant temperature of 45 ℃, is charged to 4.4V (LiNi 0.5Co0.2Mn0.3O2/SiO-C) with constant current of 1 ℃, is charged to 0.05C with constant current and constant voltage, is discharged to 2.75V with constant current of 1C, and is circulated in this way, the discharge capacity and the impedance of the 1 st circle and the discharge capacity and the impedance of the last circle are recorded, and the initial battery volume and the volume after 800 circles of circulation of the battery are measured.
The capacity retention, resistance increase and air expansion rate of the high temperature cycle were calculated as follows:
Capacity retention = discharge capacity of last round/1 st round capacitance x 100%;
Impedance increase rate= (impedance of last turn-impedance of 1 st turn)/impedance of 1 st turn×100%;
Air expansion ratio= (battery volume after cycling-initial battery volume)/initial battery volume x 100%.
The test results obtained in 1.1, examples 1 to 23 and comparative examples 1 to 12 are filled in Table 1.
TABLE 1
As can be seen from the test results of table 1, when the mass percentage of silicon element in the anode active material is 2-50%, and the compound shown in structural formula 1 is used as the additive, the additive amount is 0.01-5.0%, the capacity retention rate of the battery is greatly improved compared with the battery without the compound shown in structural formula 1, and meanwhile, the impedance growth rate and the air expansion rate are remarkably reduced. It is shown that the addition of the compound shown in the structural formula 1 to the nonaqueous electrolyte can better improve the cycle performance of the battery in a larger range. As can be seen from comparative examples 1 to 4, when the mass percentage of silicon element in the negative electrode active material is 2 to 50%, the capacity of the battery without the compound shown in structural formula 1 is greatly reduced, and water jump occurs, which is a non-linear reduction process of discharge capacity of the lithium ion battery in a cycle process, and is characterized in that the capacity of the battery is greatly reduced in a short time. As can be seen from comparative examples 5 to 12, when the silicon element content in the anode active material is more than 50% by mass, the battery cycle performance is not improved even if 0.01 to 5.0% of the compound represented by structural formula 1 is added.
Meanwhile, according to the data of examples 1-23, although the content of the compound shown in the structural formula 1 is improved, the improvement of the battery cycle performance is not in a linear relationship, which indicates that the improvement of the battery performance is related to the content of the compound shown in the structural formula 1 and the silicon element mass percent content in the anode active material, and only if the content of the compound and the silicon element mass percent content are coordinated within a certain range, the improvement of the battery can be obviously achieved.
1.2, Examples 24 to 35 and comparative example 1 are filled in Table 2.
TABLE 2
As can be seen from the test results of Table 2, the mass percentage (T%) of silicon element in the negative electrode active materials of examples 24 to 29 is in the range of 2 to 10%, the mass percentage (T%) of the silicon element in the negative electrode active materials of examples 30 to 35 is also in the range of 2 to 10%, but the mass percentage (T%) of the silicon element in the negative electrode active materials of examples 30 to 35 is more than 3%, and the test results show that the minimum capacity retention rate of examples 24 to 29 can reach 73.1%, the maximum capacity retention rate of examples 30 to 35 is only 75.1%, the minimum capacity retention rate is only 63.6%, and the impedance growth rate and the air expansion rate of examples 24 to 29 are generally lower than those of examples 30 to 35. When the mass percentage of silicon element in the anode active material is between 2% and 10%, the addition of a proper amount of electrolyte containing 0.01% to 3% of the compound shown in the structural formula 1 can effectively improve the high-temperature cycle performance of the battery, and when the addition amount is 3% to 5%, the impedance is increased due to an interface film formed by the compound shown in the structural formula 1, and the cycle performance is reduced. The method shows that when the mass percentage (T%) of silicon element in the anode active material is 2-10%, and the content of the compound shown in the structural formula 1 is 0.01-3%, the method has a remarkable effect on improving the cycle performance of the battery.
1.3, Examples 11, 12, 36 to 44 and comparative example 13 are filled in Table 3.
TABLE 3 Table 3
As can be seen from the test results in Table 3, the negative electrode active materials of examples 11, 12 and 36 to 39 each have a silicon element content by mass (T%) within a range of 10 to 50% and the compound represented by structural formula 1 each has a silicon element content by mass (T%) within a range of 10 to 50% and the negative electrode active materials of examples 40 to 44 each have a silicon element content by mass (T%) within a range of 10 to 50% but the compound represented by structural formula 1 each has a content of less than 0.05%, and the test results show that the 45℃ cycle 800 capacity retention of examples 11, 12 and 36 to 39 is 70% or more and the 45℃ cycle 800 capacity retention of examples 40 to 44 is 70% or less, and that the impedance growth rate and the air expansion rate of examples 11, 12 and 36 to 39 are lower than those of examples 40 to 44 by about 20% points. When the mass percentage of silicon in the anode material is increased to 10% -50%, the optimal content of the compound shown in the structural formula 1 required for forming the complete interface film is increased, so that the cycle performance of the battery can be effectively improved when the content of the compound is 0.05% -5%. The silicon element mass percent in the anode active material is 10 percent < T less than or equal to 50 percent, and the content of the compound shown in the structural formula 1 is 0.05-5 percent, so that the impedance, the air expansion and the cycle performance of the battery are all obviously improved.
Table 4 is filled with test results obtained in 1.4, examples 11, 45 to 58 and comparative examples 1 to 4.
TABLE 4 Table 4
As can be seen from the test results in Table 4, under the condition that the mass percentage of silicon element in the anode active material is 2-50%, the cyclic performance of the battery is improved to different degrees by adopting the compounds shown in different structural formulas 1 to be added into the electrolyte.
The test results obtained in 1.5, examples 59 to 62 and comparative examples 14 to 17 are shown in Table 5.
TABLE 5
As can be seen from the data in Table 5, in examples 59 to 62, the compound of formula 1 was used in combination with a conventional additive for lithium batteries, while the compound of formula 1 was not added to comparative examples 14 to 17. Test results show that the capacity retention rate of the example 59-62 at 45 ℃ for 800 circles is obviously higher than that of the comparative examples 14-17, and meanwhile, the impedance growth rate and the air expansion rate are lower than those of the comparative examples 14-17, so that the high-temperature cycle performance of the battery can be further improved by the compound shown in the structural formula 1 and the conventional additive of the lithium battery.
In summary, the invention can remarkably improve the problems of battery cycle gas expansion, impedance increase and the like by adding the compound shown in the structural formula 1 into the nonaqueous electrolyte, reduce the generation of gas in the battery cycle process, and obviously improve the cycle capacity, and meanwhile, the inventor finds that the battery performance is not improved linearly along with the increase of the content of the compound shown in the structural formula 1 through a large amount of experiments, the improvement of the battery performance by the compound shown in the structural formula 1 is related to the mass ratio of the silicon element to the anode active material, and the compound shown in the structural formula 1 can effectively improve the cycle performance of the battery when the mass ratio of the silicon element to the anode active material is 2% -50%. Further researches show that when the mass percentage of silicon element in the anode active material is 2-10%, and the content of the compound shown in the structural formula 1 is 0.01-3%, the improvement of the battery cycle performance is achieved, and when the mass percentage of silicon element in the anode active material is 10% < T less than or equal to 50%, and the content of the compound shown in the structural formula 1 is 0.05-5%, the battery ballooning, the impedance and the cycle performance are all improved remarkably.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The lithium ion battery comprises an anode, a cathode and nonaqueous electrolyte, and is characterized in that the cathode comprises a cathode active material, the cathode active material contains a silicon-based material, and the silicon element in the silicon-based material accounts for 2-50% of the mass of the cathode active material;
the nonaqueous electrolyte comprises a solvent, electrolyte salt and an additive, wherein the solvent comprises one or more of an ether solvent, a nitrile solvent, a carbonate solvent and a carboxylate solvent, the additive comprises at least one of compounds shown as a structural formula 1, and the compounds shown as the structural formula 1 are selected from one or more of compounds 1-1 to 1-4:
The addition amount of the compound shown in the structural formula 1 is 0.01-5.0% based on 100% of the total mass of the nonaqueous electrolyte.
2. The lithium ion battery of claim 1, wherein the additive further comprises at least one of an unsaturated cyclic carbonate compound, a fluorinated cyclic carbonate compound, a sultone compound, lithium difluorophosphate, vinyl sulfate (DTD), lithium difluorosulfonimide (LiFSI).
3. The lithium ion battery according to claim 2, wherein the unsaturated cyclic carbonate compound includes at least one of Vinylene Carbonate (VC) and ethylene carbonate (VEC);
The fluorinated cyclic carbonate compound comprises fluoroethylene carbonate (FEC);
The sultone compound is at least one selected from 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS) and 1, 3-Propylene Sultone (PST).
4. A lithium ion battery according to claim 2 or 3, wherein the unsaturated cyclic carbonate compound content is 0.1 to 5% based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery, and/or
The content of the fluorinated cyclic carbonate compound is 0.1-30% based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery, and/or
And the mass percentage of the sulfonate lactone compound is 0.1-5% based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery.
5. The lithium ion battery according to claim 2, wherein the mass percentage of the lithium difluorophosphate is 0.1-2% based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery, and/or
The content of the vinyl sulfate (DTD) is 0.1-5% by mass based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery, and/or
The mass percentage content of the lithium bis (fluorosulfonyl) imide (LiFSI) is 0.1-5% based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery.
6. The lithium ion battery of claim 1, wherein the ether solvent comprises a cyclic ether or a chain ether, the cyclic ether comprising one or more of 1, 3-Dioxolane (DOL), 1, 4-Dioxane (DX), crown ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-CH 3 -THF), 2-trifluoromethyl tetrahydrofuran (2-CF 3 -THF);
The chain ether comprises one or more of Dimethoxymethane (DMM), 1, 2-Dimethoxyethane (DME) and diglyme (TEGDME);
The nitrile solvent comprises one or more of acetonitrile, glutaronitrile and malononitrile;
The carbonate solvent comprises cyclic carbonate or chain carbonate, wherein the cyclic carbonate comprises one or more of Ethylene Carbonate (EC), propylene Carbonate (PC), gamma-butyrolactone (GBL) and Butylene Carbonate (BC), and the chain carbonate comprises one or more of dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) and dipropyl carbonate (DPC);
the carboxylic ester solvent comprises one or more of Methyl Acetate (MA), ethyl Acetate (EA), propyl acetate (EP), butyl acetate, propyl Propionate (PP) and butyl propionate.
7. The lithium ion battery of claim 1, wherein the electrolyte salt comprises a lithium salt comprising one or more of LiPF6 、LiBF4 、LiBOB、LiDFOB、LiN(SO2CF3)2 、LiN(SO2C2F5)2 、LiC(SO2CF3)3 、LiN(SO2F)2 ;
In the nonaqueous electrolytic solution, the concentration of the electrolyte salt is 0.1mol/L to 8mol/L.
8. The lithium ion battery of claim 1, wherein the positive electrode comprises a positive electrode active material selected from at least one of a nickel cobalt manganese ternary material, a nickel cobalt aluminum ternary material, liFePO 4、LiCoO2、LiMnO2、LiNiMnO2, and composites thereof.
9. The lithium ion battery according to any one of claims 1 to 8, wherein the mass percentage of silicon element in the negative electrode active material is t%, and the mass percentage of the compound represented by structural formula 1 in the nonaqueous electrolyte is w%, and the following are satisfied:
t is more than or equal to 2 and less than or equal to 10, W is more than or equal to 0.01 and less than or equal to 3;
or 10< T.ltoreq.50, and 0.05.ltoreq.W.ltoreq.5.
10. The lithium ion battery of claim 1, wherein the silicon-based material is selected from at least one of a silicon material, an oxide of silicon, a silicon-carbon composite, and a silicon alloy material.
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