CN111934015A - Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte - Google Patents
Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte 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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Abstract
The invention provides a lithium ion battery non-aqueous electrolyte and a lithium ion battery containing the same, wherein the lithium ion battery non-aqueous electrolyte comprises a lithium salt, a non-aqueous organic solvent and an additive, the additive comprises a compound with a structural formula I,
Description
Technical Field
The invention relates to the field of lithium ion batteries, and relates to a lithium ion battery non-aqueous electrolyte and a lithium ion battery containing the same.
Background
The lithium ion battery has the advantages of high specific energy, no memory effect, long cycle life and the like, and is widely applied to the fields of 3C digital, electric tools, aerospace, energy storage, power automobiles and the like, and the rapid development of electronic information technology and consumer products puts higher requirements on the high voltage and high energy density of the lithium ion battery. In lithium ion batteries, high-voltage ternary positive electrode materials (NCM or NCA) are widely applied to portable electronic devices such as mobile phones and notebook computers, electric vehicles and large energy storage devices due to the advantages of high energy density, environmental friendliness, long cycle life and the like, but the energy density of batteries is higher and higher in the market, so that the commercial ternary positive electrode material lithium ion batteries are difficult to meet the use requirements.
At present, research shows that one of effective ways for improving the energy density of the ternary electrode material is to improve the working voltage of the battery, which is a trend of battery development and is also an inevitable requirement for new energy automobile development. However, after the working voltage of the ternary power battery is increased, the performances of the battery, such as charge and discharge cycles, are reduced. The reasons may be: on one hand, the anode material is not stable enough under high voltage, on the other hand, the matching performance of the electrolyte and the material is poor, and the common electrolyte can be oxidized and decomposed under the condition of high voltage, so that the battery has poor high-temperature storage performance, poor high-temperature cycle performance, poor low-temperature discharge performance and poor safety, and the consumption of the electrolyte causes low capacity and low coulombic efficiency for the first time. Therefore, the development of lithium ion battery electrolyte suitable for high-voltage ternary material system is urgent.
Disclosure of Invention
The invention aims to provide a lithium ion battery non-aqueous electrolyte and a lithium ion battery containing the same, wherein the electrolyte can improve the first coulombic efficiency, the cycle and the high-temperature performance of the battery, and is particularly suitable for the lithium ion battery under a high-voltage system.
In order to achieve the above object, the invention provides, in a first aspect, a nonaqueous electrolyte for a lithium ion battery, comprising a lithium salt, a nonaqueous organic solvent and an additive, wherein the additive comprises a compound having a structural formula I,
wherein R1 is C or N, R2 is hydrogen or an alkali metal element, and R3 and R4 are alkali metal elements. Specifically, the alkali metal elements are Li, Na, K, Rb and Cs.
Compared with the prior art, the non-aqueous electrolyte of the lithium ion battery contains the compound with the structural formula I as an additive, the additive is a nitrogen-containing heterocyclic alkali metal salt compound with a special structure, the positive electrode/electrolyte interface can be optimized under a high-voltage system with the charging voltage of 4.4V, a stable CEI film is formed on the surface of a positive electrode, the dissolution of transition metal is effectively prevented, the high-temperature performance of the battery is improved, the additive is also complexed with F & lt- & gt, HF can be effectively removed, oxygen radicals generated from a positive electrode material are absorbed, the stability of the positive electrode material is improved, and the reversibility of charge and discharge in circulation is improved. Meanwhile, hydrogen connected with the nitrogen-containing heterocyclic nitrogen is completely replaced by alkali metal elements in the additive, so that the problems of low capacity and low first coulombic efficiency caused by the fact that a large amount of active hydrogen connected with the nitrogen-containing heterocyclic nitrogen reacts with lithium ions in the electrolyte in a large amount and a large amount of lithium ions are consumed can be solved, and the lithium ions in the electrolyte are supplemented on the contrary under the condition that the lithium ions in the electrolyte are not consumed due to the introduction of excessive alkali metal ions.
For compounds having other hydrocarbyl groups linked to the nitrogen-containing heterocyclic ring of barbituric acid, such compounds are prone to hydrocarbon groups falling off from the nitrogen during the formation of the cell, and Li+Oxygen radicals are combined to generate compounds such as lithium carboxylate or lithium alkoxide, and the compounds have certain solubility in an organic solvent, so that the SEI film is unstable, the conductivity of lithium ions is reduced, and the cycle efficiency of the battery is finally reduced; on the other hand, its reaction with metallic lithium increases the irreversible capacity of the battery. The compound containing the structural formula I disclosed by the invention as an additive is in an ionic form, and on one hand, the compound is directly reacted to generate a CEI/SEI film without consuming Li in an electrolyte+In the case of (2), Li in the electrolyte is replenished+The content of the nitrogen-containing heterocyclic compound further enhances the cycling capability of the battery compared with the common nitrogen-containing heterocyclic compound; on the other hand, the decomposition of the common nitrogen heterocyclic additive at high temperature causes the risk of gas generation and further causes the reduction of capacity, and the additive is not easy to decompose after being prepared into alkali metal salts, thereby further improving the high-temperature performance of the battery. Therefore, the compound containing the structural formula I is adopted as the additive, so that the first coulombic efficiency, the cycle and the high-temperature performance of the lithium ion battery can be improved.
Furthermore, the mass percentage of the compound with the structural formula I in the electrolyte is 0.05-3%. The content of the compound of formula I may be, but is not limited to, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, preferably 0.05-0.5%.
Further, the compound with the structural formula I can be split into two structural formulas of a formula II and a formula III,
wherein R1 is C or N, R2 is hydrogen or an alkali metal element, and R3 and R4 are alkali metal elements. Specifically, the alkali metal elements are Li, Na, K, Rb and Cs. When R1 is C, R2 is hydrogen, and when R1 is N, R2 is an alkali metal element, i.e., the alkali metal element replaces all the hydrogens attached to the heterocyclic nitrogen.
Wherein R3 and R4 are alkali metal elements. Specifically, the alkali metal elements are Li, Na, K, Rb and Cs.
Further, the compound with the structural formula I is selected from at least one of the following formulas 1 to 6,
some representative compound synthetic routes are shown below, and other compounds can be obtained by reacting the corresponding cyclic lactam compound with a metal hydroxide, according to the routes.
Further, the lithium salt is selected from LiPF6、LiBF4、LiClO4、LiBOB、LiDFOB、LiFAP、LiAsF6、LiSbF6、LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2C4F9)2、LiC(SO2CF3)3、LiPF2(C2O4)2、LiPF4(C2O4)、LiB(CF3)4And LiBF3(C2F5) At least one of (1). The concentration of the lithium salt in the nonaqueous electrolyte solution is 0.5 to 2.5 mol/L. Preferably, the lithium salt is LiPF6Or LiPF6And other lithium salts.
Further, the non-aqueous organic solvent is selected from at least one of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, butyl acetate, gamma-butyrolactone, propyl propionate, ethyl propionate and ethyl butyrate.
The electrolyte further comprises 0.3-10.5% by mass of an auxiliary agent in the electrolyte, wherein the auxiliary agent is selected from at least one of 2,2, 2-trifluoroethyl carbonate, 2,2, 2-trifluoropropyl carbonate, fluoroethylene carbonate (FEC), Vinylene Carbonate (VC), diethyl pyrocarbonate, 1, 3-Propane Sultone (PS), vinyl sulfate (DTD), 1, 2-difluorovinyl carbonate, tris (trimethylsilane) phosphate, tris (trimethylsilane) phosphite, 4 '-bi-1, 3-dioxolane-2, 2' -dione (BDC), 3-divinyl bissulfate and 4, 4-divinyl bissulfate. Preferably, the auxiliary agent is at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, tris (trimethylsilane) phosphate, tris (trimethylsilane) phosphite, 4 '-bi-1, 3-dioxolane-2, 2' -dione, 3-vinyl biculfate and 4, 4-vinyl biculfate. The additives can form a stable passive film on the surface of the positive electrode, prevent the electrolyte from being oxidized and decomposed on the surface of the positive electrode, inhibit the transition metal ions from being dissolved out of the positive electrode, improve the stability of the structure and the interface of the positive electrode material, and further obviously improve the high-temperature performance and the cycle performance of the battery.
The invention also provides a lithium ion battery which comprises a positive electrode material, a negative electrode material and an electrolyte, wherein the electrolyte is the lithium ion battery non-aqueous electrolyte, and the highest charging voltage is 4.4V. The cathode material is Li(1+a)NixCoyMzN1-x-y-zO2+bWherein M is Mn or Al, N is one or more of Mg, Cu, Zn, Sn, B, Ga, Cr, Sr, Ba, V and Ti, a is more than or equal to-0.10 and less than or equal to 0.50, x is more than 0 and less than 1, y is more than 0 and less than 1, 0 and less than or equal to 0<z is less than 1, x + y + z is more than 0.7 and less than or equal to 1, and b is more than or equal to 0.05 and less than or equal to 0.10. Preferably, Li(1+a)NixCoyMzN1-x-y-zO2+bThe material can be LiNi doped with Mg, Ti and V0.8Co0.15Al0.05O2、LiNi0.8Co0.1Mn0.1O2、LiNi1/3Mn1/3Co1/3O2、LiNi0.5Mn0.3Co0.2O2、LiNi0.4Mn0.4Co0.2O2And more preferably is high-nickel ternary material LiNi0.8Co0.15Al0.05O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Mn0.3Co0.2O2. The negative electrode material is selected from at least one of artificial graphite, natural graphite, Si and alloy thereof, Sn and alloy thereof, metallic lithium and alloy thereof and lithium titanate. The electrolyte of the lithium ion battery contains the compound with the structural formula I as an additive, and is beneficial to improving the first coulombic efficiency, the cycle and the high-temperature performance of the lithium ion battery.
Detailed Description
To better illustrate the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention, and should not be taken as a limitation of the present invention.
Example 1
In a nitrogen-filled glove box (O)2＜2ppm，H2O < 3ppm), dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate are uniformly mixed according to the mass ratio of 3:5:2 to prepare 79.7g of a nonaqueous organic solvent, and 0.3g of formula 1 is added as an additive to prepare a mixed solution. Sealing, packaging, freezing at a freezing room (-4 deg.C) for 2 hr, taking out, and placing in a nitrogen-filled glove box (O)2＜2ppm，H2O is less than 3ppm), 20g of lithium hexafluorophosphate is slowly added into the mixed solution, and the electrolyte is prepared after uniform mixing.
The formulations of the electrolytes of examples 2 to 16 and comparative examples 1 to 6 are shown in Table 1, and the procedure for preparing the electrolyte is the same as that of example 1.
TABLE 1 electrolyte Components of the examples
The lithium ion battery is prepared by using the NCM523 with the highest charging voltage of 4.4V as a positive electrode material and natural graphite as a negative electrode material and using the electrolytes of examples 1 to 16 and comparative examples 1 to 6 according to the following lithium battery preparation method, and the initial coulombic efficiency test, the normal-temperature cycle performance, the high-temperature cycle performance and the high-temperature storage test are respectively carried out under the following test conditions, and the test results are shown in Table 2.
The preparation method of the lithium battery comprises the following steps:
1. preparation of positive plate
LiNi prepared from nickel cobalt lithium manganate ternary material0.5Mn0.3Co0.2O2Uniformly mixing the conductive agent SuperP, the adhesive PVDF and the Carbon Nano Tubes (CNT) according to the mass ratio of 97.5:1.5:1:1 to prepare lithium ion battery anode slurry with certain viscosity, and coating the lithium ion battery anode slurry on an aluminum foil for a current collector, wherein the coating weight is 324g/m2Drying at 85 ℃ and then carrying out cold pressing; and then trimming, cutting into pieces, slitting, drying for 4h at 85 ℃ under a vacuum condition after slitting, and welding tabs to prepare the lithium ion battery positive plate meeting the requirements.
2. Preparing a negative plate: preparing natural graphite, a conductive agent SuperP, a thickening agent CMC and a bonding agent SBR (styrene butadiene rubber emulsion) into slurry according to the mass ratio of 95:1.4:1.4:2.2, coating the slurry on a current collector copper foil, and drying at 85 ℃, wherein the coating weight is 168g/m2(ii) a And (3) cutting edges, cutting pieces, slitting, drying for 4h at 110 ℃ under a vacuum condition after slitting, and welding tabs to prepare the lithium ion battery negative plate meeting the requirements.
3. Preparing a lithium ion battery: the positive plate, the negative plate and the diaphragm prepared by the process are manufactured into a lithium ion battery with the thickness of 4.7mm, the width of 55mm and the length of 60mm by a lamination process, the lithium ion battery is baked for 10 hours at 75 ℃, and the nonaqueous electrolyte of the embodiment 16 and the comparative examples 1-5 is injected. After standing for 24h, the mixture was charged to 4.45V with a constant current of 0.lC (180mA), and then charged at a constant voltage of 4.45V until the current dropped to 0.05C (90 mA); then discharging to 3.0V with 0.2C (180mA), repeating the charging and discharging for 2 times, finally charging the battery to 3.8V with 0.2C (180mA), and finishing the manufacture of the battery.
The first coulombic efficiency test:
and (2) placing the lithium ion battery after liquid injection and aging into a polymer high-temperature clamp formation cabinet for formation, recording the formation capacity, performing secondary sealing on the battery by using a rotary shaft air-extraction sealing machine after the formation is finished, and then performing capacity grading on the battery, wherein the capacity grading step comprises the steps of charging to 4.4V at a constant current of 0.5C, then charging to 0.05C at a constant voltage until the current is reduced to 0.05C, recording the capacity grading, then discharging to 3.0V at a constant current of 0.5C, and recording the discharge capacity.
First coulombic efficiency (formation capacity + partial capacity)/discharge capacity
And (3) testing the normal-temperature cycle performance:
and (3) placing the lithium ion battery in an environment at 25 ℃, carrying out constant current charging to 4.4V at a current of 1C, then carrying out constant voltage charging until the current is reduced to 0.05C, then carrying out constant current discharging to 3.0V at a current of 1C, and recording the discharge capacity of the first circle and the discharge capacity of the last circle in such a circulating manner.
Capacity retention rate ═ last cycle discharge capacity/first cycle discharge capacity × 100%
And (3) testing high-temperature cycle performance:
and (3) placing the battery in an oven with a constant temperature of 45 ℃, charging the battery to 4.4V at a constant current of 1C, then charging the battery at a constant voltage until the current is reduced to 0.05C, then discharging the battery to 3.0V at a constant current of 1C, and repeating the steps to record the discharge capacity of the first circle and the discharge capacity of the last circle.
Capacity retention rate ═ last cycle discharge capacity/first cycle discharge capacity × 100%
High temperature storage test
And (3) charging the formed battery to 4.4V at a constant current and a constant voltage of 1C at normal temperature, measuring the initial discharge capacity and the initial battery thickness of the battery, then storing the battery for 15 days at 60 ℃, discharging the battery to 3.0V at 1C, and measuring the capacity retention and recovery capacity of the battery and the thickness of the battery after storage. The calculation formula is as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
battery capacity recovery (%) — recovery capacity/initial capacity × 100%;
TABLE 2 first coulombic efficiency, cycle and high temperature storage performance test results
(Note: the retention of the upper surface capacity of less than 50% is called severe diving)
From the results in table 2, it can be seen that the first coulombic efficiency, the high-temperature and normal-temperature cycle performance, and the high-temperature storage performance of examples 1 to 16 are all at better levels than those of comparative examples 1 to 6. The non-aqueous electrolyte of the lithium ion battery contains the compound with the structural formula I as an additive, the additive is a nitrogen-containing heterocyclic alkali metal salt compound with a special structure, the positive electrode/electrolyte interface can be optimized under a high-voltage system with the charging voltage of 4.4V, a stable CEI film is formed on the surface of the positive electrode, the dissolution of transition metal is effectively prevented, and therefore the high-temperature performance of the battery is improved. Meanwhile, hydrogen connected with the nitrogen-containing heterocyclic nitrogen is completely replaced by alkali metal elements in the additive, so that the problems of low capacity and low first coulombic efficiency caused by the fact that a large amount of active hydrogen connected with the nitrogen-containing heterocyclic nitrogen reacts with lithium ions in the electrolyte in a large amount and a large amount of lithium ions are consumed can be solved, and the lithium ions in the electrolyte are supplemented on the contrary under the condition that the lithium ions in the electrolyte are not consumed due to the introduction of excessive alkali metal ions. The compound containing the structural formula I as an additive is in an ionic form, and on one hand, the compound directly reacts to generate a CEI/SEI film without consuming Li in electrolyte+In the case of (2), Li in the electrolyte is replenished+The content of the nitrogen-containing heterocyclic compound further enhances the cycling capability of the battery compared with the common nitrogen-containing heterocyclic compound; on the other hand, gas evolution is caused by decomposition of the conventional nitrogen-containing heterocyclic additive at high temperatureFurther reducing capacity, and the additive is not easily decomposed after being prepared into alkali metal salts, further improving the high-temperature performance of the battery.
Furthermore, it can be seen from comparison of example 1 with examples 9-16 that the addition of certain adjuvants to the nitrogen-containing heterocyclic alkali metal salt additives of the formula I provides better cycle performance and better high temperature performance.
It can be seen from the comparison of example 1 and comparative examples 4 and 5 that the additive of the alkali metal salt of nitrogen-containing heterocycle having the structural formula of formula I can significantly improve the first coulombic efficiency and the cycle and high temperature performance of the battery compared with the common additive of nitrogen-containing heterocycle.
Comparing example 1 with comparative example 6, since methyl is linked to the nitrogen-containing heterocyclic nitrogen in 1, 3-dimethyl barbituric acid of comparative example 6, the methyl group on the nitrogen is liable to be dropped off at the formation stage of the battery, and Li+Oxygen radicals are combined to generate compounds such as lithium carboxylate or lithium alkoxide, and the compounds have certain solubility in an organic solvent, so that the SEI film is unstable, the conductivity of lithium ions is reduced, and the cycle efficiency of the battery is finally reduced; on the other hand, its reaction with metallic lithium increases the irreversible capacity of the battery, so that both the cycle and high-temperature performance are inferior to those of example 1.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A lithium ion battery non-aqueous electrolyte comprises lithium salt, a non-aqueous organic solvent and an additive, and is characterized in that the additive comprises a compound with a structural formula I,
wherein R1 is C or N, R2 is hydrogen or an alkali metal element, and R3 and R4 are alkali metal elements.
2. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the mass percentage of the compound having the structural formula of formula I in the electrolyte solution is 0.05-3%.
3. The nonaqueous electrolyte solution for lithium ion batteries according to claim 2, wherein the mass percentage of the compound having the structural formula of formula I in the electrolyte solution is 0.05-0.5%.
4. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the compound having the structural formula of formula I is at least one compound selected from the following formulae 1 to 6,
5. the nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the lithium salt is selected from LiPF6、LiBF4、LiClO4、LiBOB、LiDFOB、LiFAP、LiAsF6、LiSbF6、LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiN(SO2C4F9)2、LiC(SO2CF3)3、LiPF2(C2O4)2、LiPF4(C2O4)、LiB(CF3)4And LiBF3(C2F5) At least one of (1).
6. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the nonaqueous organic solvent is at least one selected from the group consisting of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propylene carbonate, butyl acetate, γ -butyrolactone, propyl propionate, ethyl propionate, and ethyl butyrate.
7. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, further comprising 0.3 to 10.5% by mass of an auxiliary agent, the auxiliary agent is at least one selected from 2,2, 2-trifluoroethyl carbonate, 2,2, 2-diethyl trifluorocarbonate, 2,2, 2-ethylpropyl trifluorocarbonate, fluoroethylene carbonate, vinylene carbonate, diethyl pyrocarbonate, 1, 3-propane sultone, vinyl sulfate, 1, 2-difluoroethylene carbonate, tris (trimethylsilane) phosphate, tris (trimethylsilane) phosphite, 4 '-bi-1, 3-dioxolane-2, 2' -dione, 3-divinyl bissulfate and 4, 4-vinyl bissulfate.
8. The nonaqueous electrolyte solution for lithium ion batteries according to claim 7, wherein the auxiliary agent is at least one of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, vinyl sulfate, tris (trimethylsilane) phosphate, tris (trimethylsilane) phosphite, 4 '-bi-1, 3-dioxolane-2, 2' -dione, vinyl 3, 3-bisulphate and vinyl 4, 4-bisulphate.
9. A lithium ion battery comprising a positive electrode material, a negative electrode material and an electrolyte, wherein the electrolyte is the lithium ion battery nonaqueous electrolyte according to any one of claims 1 to 8, and the maximum charging voltage is 4.4V.
10. The lithium ion battery of claim 9, wherein the positive electrode material is Li(1+a)NixCoyMzN1-x-y-zO2+bWherein M is Mn or Al, N is one or more of Mg, Cu, Zn, Sn, B, Ga, Cr, Sr, Ba, V and Ti, a is more than or equal to-0.10 and less than or equal to 0.50, x is more than 0 and less than 1, y is more than 0 and less than 1, 0 and less than or equal to 0<z＜1，0.7＜x+y+z≤1，-0.05≤b≤0.10。
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| CN112467218A (en) * | 2020-12-01 | 2021-03-09 | 郑州大学 | Lithium metal battery based on copper nitrate electrolyte additive |
| CN114989059A (en) * | 2022-07-22 | 2022-09-02 | 山东海科创新研究院有限公司 | Lithium ion battery lithium supplement agent and preparation method and application thereof |
| CN116706230A (en) * | 2022-02-25 | 2023-09-05 | 浙江大学 | High-voltage electrolyte for lithium battery |
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