CN113675474B - Novel phosphorus-containing high-safety electrolyte and lithium ion battery - Google Patents
Novel phosphorus-containing high-safety electrolyte and lithium ion battery Download PDFInfo
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- CN113675474B CN113675474B CN202110968507.6A CN202110968507A CN113675474B CN 113675474 B CN113675474 B CN 113675474B CN 202110968507 A CN202110968507 A CN 202110968507A CN 113675474 B CN113675474 B CN 113675474B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0566—Liquid materials
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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Abstract
The invention belongs to the technical field of lithium ion battery materials, and discloses a novel phosphorus-containing high-safety electrolyte and a lithium ion battery. The high temperature resistant additive has a structure shown as formula I, wherein R is 1 、R 2 Each independently selected from the group consisting of-H, -F, cyano, fluoro substituted or unsubstituted C2 to C6 alkyl, fluoro substituted or unsubstituted C2 to C6 alkenyl, fluoro substituted or unsubstituted C2 to C6 alkynyl, fluoro substituted or unsubstituted C2 to C6 alkoxy, fluoro substituted or unsubstituted C2 to C6 amino, fluoro substituted or unsubstituted C6 to C12 aryl, and fluoro substituted or unsubstituted C5 to C12 heterocyclyl. The electrolyte added with the high-temperature resistant additive can improve the flame retardance, obviously improve the high-temperature cycle performance of the high-nickel ternary lithium ion battery and inhibit gas generation in the cycle process.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a novel phosphorus-containing high-safety electrolyte and a lithium ion battery.
Background
The three elements essential to the combustion process are fuel, heat and oxygen, and the maintenance of the combustion process generally relies on the production of free radicals. The combustion process can be carried out in a simple overview of the following 4 steps:
O 2 + hot → O 2 *
Fuel + heat → H
O 2 *+H·→HOO*·
HOO*·→2HO·+O 2
Hydrogen radical (H), singlet oxygen (O) 2 * ) And hydroxyl radicals (HO ·) are very reactive and generate a lot of heat (flame) and thus play a very important role in maintaining combustion.
High-nickel ternary lithium ion batteryThe high-temperature performance is poor, and the gas is easy to generate in the high-temperature circulation process at 45 ℃, so that the safety performance and the service life of the battery are influenced. The worse the thermal stability of the structure of the ternary material along with the increase of the nickel content, the greater the safety risk, and the more Ni 3+/4+ And the energy band is overlapped with O, so that in a lithium-removing state, crystal lattice O can be removed from the crystal lattice, and once the battery is impacted, short circuit and ignited, oxygen can support combustion.
Patent CN 109687010A discloses a ternary high nickel electrolyte, which can improve the high temperature cycle performance and the high temperature storage life of a lithium ion battery by adding an additive tris (trimethylsilyl) phosphorus compound into the electrolyte, wherein the tris (trimethylsilyl) phosphorus compound significantly reduces the interface impedance of the positive electrode, which is beneficial to the 36800migration of lithium ions at the positive electrode interface, effectively reduces the oxidation activity of a high nickel positive electrode material to the electrolyte, particularly the oxidation of the high nickel positive electrode material to the electrolyte under a high temperature condition, can inhibit the dissolution of transition metals such as nickel, cobalt and the like caused by the change of the structure of the high nickel positive electrode material due to the reduction reaction, and improve the high temperature cycle performance and the high temperature storage life of the lithium ion battery.
Patent CN 109193029A discloses a high-nickel ternary lithium ion battery non-aqueous electrolyte, which can form a layer of uniform and compact protective film on the surface of a ternary material by adding a phosphate compound containing a structure shown in formula (1) as a film-forming additive, so as to reduce the oxidation reaction of the electrolyte on the surface of the battery material; meanwhile, corrosion of HF to NCM particles is inhibited, cracks in the NCM particles in the circulation process are avoided, and dissolution of transition metal elements at high temperature is reduced; the additive can also be reduced on the surface of the negative electrode material to form an SEI film.
Patent CN 112290090A discloses a high-nickel ternary lithium ion battery non-aqueous electrolyte, which can form an interface protective film on the surface of a positive electrode material by adding a film-forming additive containing a phosphorus-based compound represented by formula (2), reduce the oxidative decomposition of the electrolyte, inhibit the dissolution of positive electrode metal ions, and contribute to improving the high-temperature cycle performance and the high-temperature storage performance of the battery.
However, the above phosphorus-based compounds are liable to react or undergo ring-opening under strong acidic, strong basic or strong oxidizing conditions to form new substances, and their stability is slightly poor.
The pentaerythritol diphosphonate compound is mainly used as a flame retardant additive of a high polymer material, but is rarely applied to lithium ion battery electrolyte at present, and particularly has no corresponding report on the aspects of improving the high-temperature cycle performance of a high-nickel ternary lithium ion battery and inhibiting gas generation in the cycle process while improving the flame retardance.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a novel phosphorus-containing high-safety electrolyte.
The invention also aims to provide a high-nickel ternary lithium ion battery containing the electrolyte.
The purpose of the invention is realized by the following technical scheme:
a novel phosphorus-containing high-safety electrolyte comprises a solvent, a lithium salt and a high-temperature-resistant additive, wherein the high-temperature-resistant additive has a structure shown as the following formula I:
in the formula R 1 、R 2 Each independently selected from-H, -F, cyano, fluoro substituted or unsubstituted C2-C6 alkyl, fluoro substituted or unsubstituted C2-C6 alkenyl, fluoro substituted or unsubstituted C2-C6 alkynyl, fluoro substituted or unsubstituted C2-C6 alkoxy, fluoro substituted or unsubstituted C2-C6 amino, fluoro substituted or unsubstituted C6-C12 aryl, and fluoro substituted or unsubstituted C5-C12 heterocyclyl.
Further preferably, the high temperature resistant additive has any one of the structures shown in the following formulas 1 to 8:
still more preferably, the high temperature resistant additive has a structure as shown in formula 1 below:
further, the addition amount of the high-temperature resistant additive accounts for 0.1-20.0% of the total mass of the electrolyte.
Further, the solvent is a carbonate solvent system, and comprises at least one of ethylene carbonate, propylene carbonate, fluoroethylene carbonate, gamma-butyrolactone, gamma-valerolactone, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, propyl propionate, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate and methyl butyrate.
Further, the lithium salt is LiBOB or LiPF 6 、LiBF 4 、LiSbF 6 、LiClO 4 、LiCF 3 SO 3 、Li(CF 3 SO 2 ) 2 N、LiC 4 F 9 SO 3 、LiAlO 4 、LiAsF 6 、LiAlCl 4 At least one of LiFSI, liTFSI and lithium carbonate with low fatty acid; the concentration of the lithium salt in the electrolyte is 0.1-1.5M.
Further, the electrolyte also comprises an auxiliary additive; the auxiliary additive is at least one of 1, 3-propane sultone, 1, 4-butane sultone, propenyl-1, 3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate, fluoroethylene carbonate, lithium bis-fluorosulfonyl imide, lithium difluoro oxalate borate, lithium difluoro oxalate phosphate, lithium difluoro phosphate and lithium tetrafluoroborate; the auxiliary additive 1, 3-propane sultone, 1, 4-butane sultone, propenyl-1, 3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate or fluoroethylene carbonate accounts for 0.1-3.0% of the total mass of the electrolyte; the auxiliary additive is lithium bis (fluorosulfonyl) imide, lithium difluoro (oxalato) borate, lithium difluoro (oxalato) phosphate, lithium difluoro (phosphates) or lithium tetrafluoroborate, and accounts for 0-1.0M of the total mass of the electrolyte.
A high-nickel ternary lithium ion battery is composed of a high-nickel ternary material anode, a high-nickel ternary material cathode, a high-nickel ternary material diaphragm and the electrolyte.
Compared with the prior art, the invention has the beneficial effects that:
(1) The high-temperature resistant additive can form a stable CEI film on the surface of the positive electrode and prevent Ni with strong oxidizing property 3+ Further oxidizing with electrolyte and preventing the decomposition of the SEI film of the negative electrode, thereby inhibiting the high-temperature gas production of the lithium ion battery, effectively improving the high-temperature cycle performance at 45 ℃ and inhibiting the gas production in the cycle process.
(2) The high temperature resistant additive achieves the purpose of flame retardance by capturing free radicals, and when the phosphorus-containing substance is heated, a large amount of combustion free radicals (H, O) capable of capturing gas phase are released 2 * HO.), thereby blocking the chain reaction of the free radicals and improving the safety performance of the battery.
(3) Compared with the phosphorus-based compound applied to the lithium ion battery electrolyte in the prior art, the pentaerythritol diphosphonate compound has better stability, the six-membered ring structure of the pentaerythritol diphosphonate compound has good stability and is not easy to open the ring, the reactive phosphorus hydroxyl group of the pentaerythritol diphosphonate compound is sealed by the substituent group, the structural stability of the pentaerythritol diphosphonate compound is further enhanced, and the high-temperature resistant additive can resist strong acid, strong base or strong oxidizing conditions, so that the high-temperature cycle performance of the electrolyte is improved and the thickness expansion performance of the electrolyte is inhibited. Particularly, in the case of blocking with fluorine-substituted alkyl, the improvement effect is more remarkable.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Examples 1 to 27
The electrolyte compositions of examples 1 to 27 and comparative examples 1 to 3 were designed as shown in table 1 below. The structures of the high-temperature resistant additives A1 to A8 and the structures of the high-temperature resistant additives A9 to A10 in comparative examples are shown below.
TABLE 1 electrolyte Components and additive ratios
The preparation method of the high-nickel ternary lithium ion battery comprises the following steps:
and determining the coating surface density according to the capacity design (2000 mAh) of the battery and the capacities of the positive and negative electrode materials. The positive active substance is a high-nickel ternary material purchased from Guizhou Zhenhua or Shenzhen fibrate Rui; the negative active material is artificial graphite purchased from Shenzhen fibrate; the diaphragm is a PE coated ceramic diaphragm which is purchased from a star source material and has the thickness of 20 mu m.
The preparation steps of the anode are as follows: mixing a high-nickel ternary material, conductive carbon black and a binder polyvinylidene fluoride according to a mass ratio of 96.8.
The preparation steps of the cathode are as follows: mixing graphite, conductive carbon black, binder styrene-butadiene rubber and carboxymethyl cellulose according to a mass ratio of 95.5.
The high-nickel ternary lithium ion battery assembly steps are as follows: and winding the positive pole piece, the negative pole piece and the PE ceramic diaphragm to obtain a battery core, placing the battery core into an aluminum plastic film for packaging, drying, injecting an electrolyte for sealing, standing, forming, secondary sealing, capacity grading and the like to obtain the lithium ion battery.
Preparing an electrolyte: in a glove box filled with argon, ethylene Carbonate (EC), diethyl carbonate (DEC) and dimethyl carbonate (EMC) were mixed in the weight ratio EC: and (4) DEC: 1, EMC =1, the mass percentage of the solvent is 74.5% to 87.5% of the total mass of the electrolyte, lithium hexafluorophosphate is used as the lithium salt, the mass fraction thereof is 12.5% (1 mol/L) of the total mass of the electrolyte, 0-3% of vc, 0-4% of fec, 0-3% of ps are added, 0-1M LiFSI is added. Additives were added to the electrolyte compositions shown in table 1, wherein the additive ratio was a ratio based on the total weight of the electrolyte.
(1) And (3) testing the cycle performance of the lithium ion battery at high temperature:
at 45 ℃, the lithium ion battery is charged to a voltage of 4.2V at a constant current of 1C, charged at a constant voltage until the current is 0.05C, then discharged to a voltage of 2.75V at a constant current of 1C, and subjected to a 500-cycle charge-discharge test to detect the discharge capacity of the 500 th cycle.
Capacity retention rate = (500 th discharge capacity/first discharge capacity) × 100%.
Before circulation at 45 ℃, charging the lithium ion battery at normal temperature by a constant current of 1C until the voltage is 4.2V, and at a constant voltage of 4.2V until the current is 0.05C, and recording the thickness of the lithium ion battery to be tested as H0; taking out after circulation for 500 weeks at 45 ℃, standing for 6 hours at normal temperature, and then testing the thickness, and recording as H1;
thickness expansion ratio (%) = (H1-H0)/H0 × 100%.
(2) And (3) testing the self-extinguishing time of the electrolyte:
taking a PP or PE diaphragm with the length-width size = 20cm-40cm, completely soaking the diaphragm into an electrolyte sample for 5min, then taking out the diaphragm soaked in the electrolyte by using tweezers, igniting the diaphragm soaked in the electrolyte by using an igniter, and recording the combustion condition of the diaphragm soaked in the electrolyte and the time from the combustion to the automatic extinguishing.
The capacity retention rate at 45 ℃ in 500 cycles, the thickness expansion rate and the self-extinguishing time of the electrolyte of the above examples and comparative examples are shown in the following table 2.
TABLE 2 retention of cyclic capacity, rate of thickness expansion and time to self-extinguishment
The following are shown in examples 1 to 10: with the addition of the additive A1 increasing by 0.1-20%, under the charge cut-off voltage of 4.2V, the cycle capacity retention rate at 45 ℃ and 1C shows a trend of increasing and then decreasing. When the addition amount of the A1 is 0.5%, the performance is optimal, and compared with the comparative example 1, the cycle performance at 45 ℃ of the A1 added with 0.5% is obviously superior to that of a comparative group, the cycle performance is improved by nearly 100%, and the thickness expansion rate is reduced by 7%, which shows that the improvement of the cycle performance of the battery, the inhibition effect of the thickness expansion and the improvement of the flame retardant property are very obvious when the high-temperature resistant additive is added.
As can be seen from examples 11 to 17: the additive A with different substituent structures can improve the high-temperature cycle performance and inhibit the thickness expansion. When the structure of the additive is A1, namely the substituent is trifluoromethyl, the optimal cycle performance, thickness expansion rate performance and flame retardant property can be achieved. And as can be seen from comparison with comparative examples 2 and 3, the improvement effect of the high temperature resistant additive of the present invention is a result of the combined action of the six-membered ring structure and the closed substituent. Compared with a cyclic phosphate structure without a closed substituent and a common phosphate structure without a cyclic structure, the high-temperature resistant additive has better cycle performance, thickness expansion inhibition performance and flame retardance.
It can be seen from examples 18 to 27 that: the selection and addition of the lithium salt, the solvent and the auxiliary additive have little influence on the performance of the battery. The key factor affecting performance is the high temperature resistant additive of the present invention.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A high-nickel ternary lithium ion battery is characterized by comprising a high-nickel ternary material anode, a high-nickel ternary material cathode, a high-nickel ternary material diaphragm and electrolyte; the electrolyte comprises a solvent, lithium salt and a high-temperature resistant additive, wherein the high-temperature resistant additive has any one structure shown in the following formulas 1-8:
the addition amount of the high-temperature resistant additive accounts for 0.5 percent of the total mass of the electrolyte;
the solvent is a mixture of EC, DEC and EMC with a volume ratio of 1;
the lithium salt is LiPF 6 The concentration of the lithium salt in the electrolyte is 0.1-1M.
2. The lithium-ion battery as claimed in claim 1, wherein the refractory additive has a structure represented by formula 1:
3. the high-nickel ternary lithium ion battery of claim 1, further comprising an auxiliary additive in the electrolyte; the auxiliary additive is at least one of 1, 3-propane sultone, 1, 4-butane sultone, propenyl-1, 3-sultone, vinyl sulfate, propylene sulfate, butylene sulfite, vinylene carbonate, fluoroethylene carbonate, lithium bis-fluorosulfonyl imide, lithium difluoro oxalate borate, lithium difluoro oxalate phosphate, lithium difluoro phosphate and lithium tetrafluoroborate.
4. The high-nickel ternary lithium ion battery according to claim 3, wherein the auxiliary additive 1, 3-propane sultone, 1, 4-butane sultone, propenyl-1, 3-sultone, ethylene sulfate, propylene sulfate, butylene sulfite, vinylene carbonate or fluoroethylene carbonate accounts for 0.1-3.0% of the total mass of the electrolyte; the auxiliary additive is lithium bis (fluorosulfonyl) imide, lithium difluoro (oxalato) borate, lithium difluoro (oxalato) phosphate, lithium difluoro (phosphates) or lithium tetrafluoroborate, and accounts for 0-1.0M of the total mass of the electrolyte.
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| WO2018103335A1 (en) * | 2016-12-08 | 2018-06-14 | 宁德时代新能源科技股份有限公司 | Secondary battery and method for electrolyte injection |
| CN109065951A (en) * | 2018-07-31 | 2018-12-21 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion battery electrolytes and lithium ion battery |
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| CN109273764A (en) * | 2018-09-14 | 2019-01-25 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte |
| CN112838270B (en) * | 2021-03-18 | 2022-06-14 | 合肥国轩高科动力能源有限公司 | Electrolyte additive for improving high-temperature flatulence of battery, electrolyte and lithium ion battery containing electrolyte |
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| CN109065951A (en) * | 2018-07-31 | 2018-12-21 | 东莞市杉杉电池材料有限公司 | A kind of lithium-ion battery electrolytes and lithium ion battery |
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