CN109713367B - Silicon-containing high-energy-density lithium ion battery - Google Patents
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Abstract
The invention relates to a silicon-containing high-energy-density lithium ion battery, which comprises a positive electrode, a silicon-containing negative electrode, fluorine-containing electrolyte, a diaphragm, a lug and a packaging material, wherein the positive electrode is connected with the diaphragm; the silicon-containing negative electrode takes a silicon-based material as all or part of electrochemical active substances; the electrolyte contains lithium salt, a nonaqueous organic solvent capable of dissolving the lithium salt, SEI film forming additive and hydrofluoroether; the solubility of lithium salt in the nonaqueous organic solvent capable of dissolving lithium salt is higher than 2 mol/L; the solubility of lithium salt in said hydrofluoroether is less than 0.3 mol/L; the nonaqueous organic solvent capable of dissolving the lithium salt is mutually soluble with the hydrofluoroether; the nonaqueous organic solvent capable of dissolving the lithium salt is mutually soluble with the liquid SEI film forming additive, and can dissolve the solid SEI film forming additive. The silicon-containing lithium ion battery has the advantages of high energy density, long cycle life, good rate characteristic, high safety performance, difficult expansion and deformation and the like.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a silicon-containing high-energy-density lithium ion battery.
Background
Due to rapid development and wide application of various portable electronic devices, new energy electric vehicles and energy storage systems in recent years, demands for lithium ion batteries with high energy density, long cycle life, safe use and good rate characteristics are increasingly urgent.
The negative electrode material of the lithium ion battery which is commercialized at present is mainly graphite, but the improvement of the energy density of the lithium ion battery is limited due to the low theoretical capacity (372 mAh/g). Silicon-based anode materials have the advantage of high capacity that other anode materials cannot match, have become a heating point in recent years, and are gradually developed from laboratories to commercial applications. The silicon-based negative electrode material mainly comprises three materials, namely simple substance silicon or a composite material formed by the simple substance silicon and carbon; second, silicon oxygen compound or its composite material with carbon material; and thirdly, the alloy material consists of silicon and other metal elements. The three silicon-based negative electrode materials have the capacity which is several times that of graphite, so that the application of the silicon-based negative electrode materials in the lithium ion battery makes the further improvement of the energy density possible. However, during the charge and discharge cycles of the lithium ion battery, the continuous lithium intercalation and deintercalation process of the silicon-based negative electrode material can cause the silicon-based material particle body to actively expand and contract. Such repeated volume expansion and contraction changes may cause breakage of the particles. The surface of the fresh silicon material produced after the particles are broken and the traditional electrolyte can generate a new unstable SEI film. The repeated generation and thickening of the SEI film continuously consumes the electrolyte and the limited migratable lithium ions in the battery system, reducing the cycle performance of the battery. In addition, the SEI continuously formed and thickened on the surface of the silicon negative electrode in the cycle process of the silicon-containing lithium ion battery can also cause the internal resistance of a pole piece and the battery to be increased, and the expansion rate to be increased, so that the battery is excessively thick, deformed and even the shell of the battery is cracked.
The electrolyte currently applied to commercial graphite-based lithium ion batteries is generally lithium hexafluorophosphate (LiPF)6) The lithium salt is a mixture of a cyclic carbonate with high viscosity and high dielectric constant, such as Ethylene Carbonate (EC) and Propylene Carbonate (PC), and a chain carbonate with low viscosity and low dielectric constant, such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC), and the concentration of the lithium salt is generally 1 to 1.5 mol/L. Although the electrolyte is widely applied to graphite-based lithium ion batteries, the electrolyte has poor compatibility with silicon-based negative electrodes in silicon-containing lithium ion batteries, and a thick SEI film can be continuously formed on the surface of a silicon-based material, so that the problems of low charging and discharging efficiency, rapid increase of internal resistance, rapid water-jumping circulation, easiness in expansion and deformation and the like of the lithium ion batteries are caused. Moreover, the traditional low-concentration electrolyte has poor thermal stability and sensitivity to waterThe problems of easy decomposition of the electrolyte and the like due to the high voltage and the sensitivity to the water content of the materials used by the electrolyte and the environmental humidity in the electrolyte preparation and battery liquid injection processes are solved, the service temperature range and the voltage working window of the electrolyte are limited.
The above problems severely limit the commercial applications of silicon-containing lithium ion batteries. In view of the above problems, the following improvements have been made by researchers.
Chinese patent publication No. CN102005606B discloses a silicon-containing negative electrode lithium ion secondary battery using fluoroethylene carbonate and 1, 3-propane sultone as electrolyte additives. Chinese patent publication No. CN103594730B discloses an electrolyte for a silicon negative electrode lithium battery, which uses an organic silicon isocyanate compound containing a polyether chain as an additive, and the additive can effectively improve the charge and discharge performance of the silicon negative electrode lithium battery, reduce the occurrence of side reactions, inhibit the battery gassing, and improve the cycle life. Chinese patent publication No. CN103413969B discloses an electrolyte for a lithium ion battery using a silicon-based material as a negative electrode material, and the lithium ion battery, wherein the electrolyte includes a film-forming additive tris (pentafluorophenyl) borane, which helps to form a stable and complete SEI film on the surface of the negative electrode material, and reduces the pulverization phenomenon caused by the volume effect of silicon when the silicon-based material is used as the negative electrode material. Chinese patent publication No. CN102479973B discloses a lithium ion battery with silicon cathode, which includes an electrolyte additive of diallyl pyrophosphate. The additive can form a stable SEI film, and relieve and inhibit the reaction between the Li-Si alloy and the organic solvent. In all of the above methods, a functional additive was added to a conventional electrolyte solution (a dilute organic carbonate solution (1.0M) of lithium hexafluorophosphate (LiPF 6)). The additives have limited improvement range on the performances of the silicon-containing lithium ion battery such as cycle and the like, the high-temperature performance is poor, and the electrolyte is still flammable.
Chinese patent publication No. CN105845978B discloses a high energy density lithium ion battery using a silicon-based negative electrode, which uses a polymer electrolyte comprising a nonaqueous organic solvent, a lithium salt, an additive and a polymer dispersed in the electrolyte, wherein the polymer comprises a mixture of cellulose carboxylate and a fluorine-containing olefin polymer, and the additive comprises vinyl trialkoxysilane. The polymer electrolyte can convert the liquid electrolyte in the battery into a gel state with excellent mechanical stability and ion transmission performance after being formed at high temperature. On one hand, the adhesive property of the interface of the silicon-based negative electrode and the diaphragm can be improved, and the interface damage caused by the expansion of the silicon-based negative electrode and the consumption of electrolyte in the circulation process is avoided; on the other hand, the side reaction of the organic solvent on the active surface of the silicon-based negative electrode can be slowed down. The polymer electrolyte can improve the cycle performance of a silicon-based negative electrode lithium ion battery and reduce the thickness expansion rate of the battery in the cycle process. Chinese patent publication No. CN104868165A discloses a method for preparing a gel-state polymer lithium battery and a battery. Electrolyte containing functional additives and polymer monomers is injected into the battery cell, and the electrolyte is subjected to activation and hot-pressing polymerization to be fully soaked and polymerized to form a gel state, so that the positive pole piece, the negative pole piece and the diaphragm are adhered together to form the battery cell into a whole, wherein the diaphragm is made of a high-molecular coating layer or a ceramic coating layer. The gel state polymer lithium ion battery can remarkably improve the energy density of the battery, relieve or eliminate the performance deterioration caused by the expansion effect of the pole piece, prevent the battery core from bulging or deforming, improve the comprehensive performance of the battery and prolong the cycle life. However, the gel polymer electrolyte has low room-temperature ionic conductivity, so that the rate performance of the battery is poor, and the mechanical strength is still insufficient to inhibit the electrochemical expansion of a silicon material.
Chinese patent publication No. CN108232302A discloses a high-concentration lithium salt electrolyte suitable for a silicon-based negative electrode lithium ion battery, which comprises a lithium salt and a non-aqueous organic solvent, wherein the molar concentration of the lithium salt is 2.15-4.00 mol/L. The high-concentration electrolyte has high electrochemical stability, a compact SEI film derived from lithium salt anions is generated on the surface of the cathode, the continuous formation of the SEI film on the surface of a silicon-based cathode material is inhibited, and the stability of the interface between the silicon-based cathode and the electrolyte is improved, so that the capacity loss of the silicon-based cathode in the circulation process is reduced, and the coulombic efficiency and the circulation performance of the silicon-based cathode are improved. Compared with the traditional electrolyte with low lithium salt concentration, the high-concentration electrolyte has higher electrochemical stability because most solvent molecules are combined with lithium ions to form a solvation shell structure. However, the proportion of lithium salt in the electrolyte is too high, which significantly increases the viscosity of the electrolyte, reduces the activity of lithium ions, causes a significant decrease in the mobility of lithium ions in the electrolyte, and is also not favorable for good wetting between the electrolyte and the electrode, resulting in a low practical capacity of the battery and poor rate characteristics.
Disclosure of Invention
The invention aims to provide a silicon-containing high-energy-density lithium ion battery, which has the advantages of high energy density, long cycle life, good rate characteristic, high safety performance, difficult expansion and deformation and the like due to a special electrolyte system.
In order to achieve the purpose, the invention provides the following technical scheme:
a silicon-containing high-energy-density lithium ion battery comprises a positive electrode, a silicon-containing negative electrode, fluorine-containing electrolyte, a diaphragm, a lug and a packaging material.
The silicon-containing negative electrode takes a silicon-based material as all or part of electrochemical active substances.
The electrolyte contains lithium salt, a nonaqueous organic solvent capable of dissolving the lithium salt, SEI film forming additive and hydrofluoroether.
The solubility of lithium salt in the nonaqueous organic solvent capable of dissolving lithium salt is higher than 2 mol/L;
preferably, the solubility of the lithium salt in said non-aqueous organic solvent in which the lithium salt is soluble is higher than 3 mol/L.
The solubility of lithium salt in said hydrofluoroether is less than 0.3 mol/L;
preferably, the solubility of the lithium salt in said hydrofluoroether is less than 0.1 mol/L.
The non-aqueous organic solvent capable of dissolving the lithium salt is mutually soluble with the hydrofluoroether.
The nonaqueous organic solvent capable of dissolving the lithium salt is mutually soluble with the liquid SEI film forming additive, and can dissolve the solid SEI film forming additive.
In the fluorine-containing electrolyte, the molar concentration of lithium salt in a nonaqueous organic solvent capable of dissolving lithium salt and an additive mixture is 1-5 mol/L;
it is preferable that the molar concentration of the lithium salt in the nonaqueous organic solvent and additive mixture in which the lithium salt is soluble is 1 to 2.7 mol/L.
In the fluorine-containing electrolyte, the molar concentration of lithium salt in the whole fluorine-containing electrolyte is 0.7-4 mol/L;
preferably, the molar concentration of the lithium salt in the whole fluorine-containing electrolyte is 0.7-3 mol/L;
more preferably, the molar concentration of the lithium salt in the entire fluorine-containing electrolyte is 0.7 to 1.4 mol/L.
The mass fraction of the lithium salt is 9-68%, the mass fraction of the nonaqueous organic solvent capable of dissolving the lithium salt is 16-80%, the mass fraction of the SEI film-forming additive is 1-25%, and the mass fraction of the hydrofluoroether is 10-70%;
preferably, the mass fraction of the lithium salt is 14-48%, the mass fraction of the nonaqueous organic solvent capable of dissolving the lithium salt is 17-50%, the mass fraction of the SEI film-forming additive is 3-20%, and the mass fraction of the hydrofluoroether is 20-60%.
The hydrofluoroether is selected from at least one of the following structural general formula (1):
wherein: r1 is selected from C1-C10 fluoroalkyl;
preferably, R1 is selected from C1-C6 fluoroalkyl;
more preferably, R1 is selected from the group consisting of C1 to C3 straight chain fluoroalkyl;
wherein: r2 is selected from C1-C10 alkyl or C1-C10 fluoroalkyl,
preferably, R2 is selected from C1-C6 alkyl or C1-C6 fluoroalkyl,
more preferably, R2 is selected from the group consisting of C1-C3 alkyl and C1-C3 fluoroalkyl.
The lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium bis (oxalato) borate (LiBOB), lithium trifluoro methylsulfonate (LiSO)3CF3) Tris (trifluoromethylsulfonyl) methyllithium (LiC (CF)3SO2)3) One or more of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluoro (oxalato) borate (LiODFB);
preferably, the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium bis (oxalato) borate (LiBOB), lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (fluorosulfonyl) imide (LiFSI), lithium difluoro (oxalato) borate (LiODFB).
The non-aqueous organic solvent capable of dissolving the lithium salt is selected from one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Methyl Propyl Carbonate (MPC), dipropyl carbonate (DPC), methyl ethyl carbonate (EMC), gamma-butyrolactone (GBL), Methyl Formate (MF), Methyl Acetate (MA), Ethyl Propionate (EP), Propyl Propionate (PP) and Acetonitrile (AN);
preferably, the non-aqueous organic solvent in which the lithium salt is soluble is selected from one or more of Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), Ethyl Propionate (EP), and Propyl Propionate (PP).
The SEI film-forming additive is selected from one or more of Vinylene Carbonate (VC), ethylene carbonate (VEC), fluoroethylene carbonate (FEC), difluoroethylene carbonate (DFEC), Propylene Sulfite (PS), Ethylene Sulfite (ES), dimethyl sulfite (DMS), diethyl sulfite (DES), tris (2,2, 2-trifluoroethyl) phosphite (TTFP), 1, 3-propylene sultone (PTS), dimethyl sulfoxide (DMSO), methyl chloroformate, 1, 4-Butane Sultone (BS), ethyl methanesulfonate, butyl methanesulfonate, bromobutyrolactone, fluoroacetoxyethane, 1, 2-trifluoroacetoxyethane (BTE), anisole, N-Dimethyltrifluoroacetamide (DMTFA), chloroethylene carbonate.
Compared with the prior art, the invention has the following advantages:
1. the silicon-containing lithium ion battery uses the electrolyte specially developed for silicon-based negative electrode materials. The electrolyte has a high molar concentration of lithium salt in a mixture of a nonaqueous organic solvent in which the lithium salt is soluble and an SEI film-forming additive. Meanwhile, hydrofluoroether which is mutually soluble with the non-aqueous organic solvent is added, so that a part of the non-aqueous organic solvent for dissolving the lithium salt can be removed, the local molar concentration of the lithium salt is further improved, almost all solvent molecules and anions participate in the solvation of the lithium ions in the local area, free solvent molecules in the lithium salt local electrolyte are reduced or even completely eliminated, the complexing force of the lithium ions and the solvent molecules is enhanced, the energy barrier for reducing the solvent is improved, the reaction activity of the electrolyte is obviously reduced, the traditional electrolyte is favorably inhibited from being oxidized at a higher voltage, the traditional electrolyte can be prevented from being reduced at a lower voltage, and a stable and wider electrochemical window is obtained. The silicon negative electrode SEI film-forming additive is easier to be reduced preferentially on the surface of a negative electrode in the local high-concentration electrolyte to form a layer of SEI film with performance superior to that of the SEI film formed by the reduction of the existing electrolyte, can inhibit the further decomposition of the electrolyte, and always keeps thinner thickness and better flexibility in the circulating process, so that the conditions of obviously increased interface impedance and reduced lithium ion migration rate are avoided along with the circulation, and the higher coulombic efficiency and specific capacity can be kept in the later cycle stage of the battery. The wider electrochemical window can improve the charge cut-off voltage of the silicon-containing lithium ion battery without causing corrosion of partial lithium salt to Al foil and decomposition of a high-voltage anode to electrolyte. The use of higher voltage anode materials can lead to a greater increase in the energy density of silicon-containing cathode lithium ion batteries. The wider electrochemical window also ensures that the silicon-containing lithium ion battery does not need to be too harsh for controlling the moisture in the manufacturing process, thereby reducing the cost for controlling the manufacturing environment. The flammable solvent molecules in the high-concentration electrolyte are less, and the hydrofluoroether has a flame-retardant effect, so that the overall flammability of the electrolyte is reduced. After the high-concentration electrolyte is diluted by the hydrofluoroether, the local lithium salt concentration is further concentrated, but the electrolyte has the advantages of the traditional low-concentration lithium salt electrolyte such as low viscosity, high lithium ion conductivity, good wettability and the like.
In summary, the silicon-containing lithium ion battery provided by the invention has the advantages of high energy density, high cycle retention rate, good rate characteristic, difficulty in gas generation, difficulty in expansion, difficulty in deformation, good safety characteristic and the like.
Drawings
FIG. 1: scanning electron micrographs of the surface SEI film of the off-state negative electrode after 50 cycles of the cell in example 1.
FIG. 2: scanning electron micrograph of SEI film on surface of delithiated negative electrode after 50 cycles of battery in comparative example 1.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The hydrofluoroethers used in the following examples and comparative examples are as follows:
1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (TTE), 1,1,1,3,3, 3-hexafluoroisopropyl methyl ether (HFME), bis (2,2, 2-trifluoroethyl) ether (BTFE), decafluoro-3-methoxy-2-Trifluoromethylpentane (TMMP).
The preparation of the pure silicon cathode lithium ion battery mainly comprises the following steps:
preparing a positive plate: the mass percentage of the mixed positive active material, the conductive agent and the binding agent is 97.5:1:1.5, wherein the positive active material LiCoO2The preparation method comprises the following specific steps: weighing LiCoO in proportion2The positive electrode material, conductive carbon black and polyvinylidene fluoride (PVDF) binder powder are placed in a charging bucket, a double planetary mixer is used for premixing for 30min, then N-methyl pyrrolidone (NMP) is added as a solvent, high-speed stirring is carried out for 60min, viscous positive electrode slurry is obtained, the viscous positive electrode slurry is uniformly coated on an aluminum foil, and after drying and rolling, a pole piece is punched into small pieces with the size of 52 x 75 mm.
Preparing a negative plate: the mass percentage of the negative active material, the conductive agent, the thickening agent and the binding agent is 84.5:0.5:5:10, and the preparation process comprises the following steps: the preparation process of the pure silicon particle material of the negative active material comprises the following steps: weighing pure silicon negative electrode materials, a carbon nano tube conductive agent and sodium carboxymethylcellulose (CMC) in proportion into a charging tank, premixing for 30min by using a double planetary mixer, adding adhesives (half of Styrene Butadiene Rubber (SBR) aqueous emulsion with the concentration of 50% and half of polyacrylic acid aqueous solution with the concentration of 10%) and adding a proper amount of deionized water as a solvent, mechanically mixing to prepare viscous negative electrode slurry, uniformly coating the slurry on a copper foil, drying and rolling, and punching a pole piece into small pieces with the size of 53.5 x 76.5 mm.
Assembling the silicon-containing lithium ion battery: stacking the positive plate, the negative plate and the diaphragm prepared according to the process into a plate group according to a Z-shaped process, respectively performing pre-spot welding on positive and negative foil strips on the plate group on an ultrasonic spot welding machine, removing the length of redundant foil materials, respectively performing spot welding on an aluminum lug at the end of the positive aluminum strip, welding a nickel lug at the end point of the negative copper strip, pasting protective adhesive paper on the welded part of the lug, then packaging into an aluminum-plastic bag, performing processes such as top side sealing and sealing to prepare the plate group, aging for 24 hours at 40 ℃, injecting electrolyte and packaging, performing clamping and pressing on the battery after aging for 48 hours at 40 ℃, degassing, placing the battery in an aging box, performing capacity division (4.4V-2.75V) after aging for 48-72 hours, and then measuring the size, the weight and other performance tests.
Example 1
21.6g of EMC and 11.0g of FEC were taken, mixed uniformly, 19.4g of LiFSI was dissolved therein, and then 48.0g of TTE was added thereto and stirred uniformly. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Taking a battery, discharging until 2.75V is cut off after 50 cycles are finished, taking out the negative pole piece after disassembly, cleaning the negative pole piece for three times by using DMC, then drying in vacuum, and observing an SEI film on the surface of the pole piece under an electron microscope, wherein the SEI film formed on the surface of the negative pole piece is thin and very dense as shown in figure 1.
Example 2
17.4g of EMC and 8.9g of FEC were taken, mixed uniformly, and 15.6g of LiFSI was dissolved therein, followed by addition of 58.1g of TTE and further stirring uniformly. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Example 3
28.4g of EMC and 14.5g of FEC were taken, mixed uniformly, 25.5g of LiFSI was dissolved therein, and then 31.6g of TTE was added thereto and stirred uniformly. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Example 4
After 16.6g of EMC and 11.0g of FEC were mixed well, 24.4g of LiFSI was dissolved therein, followed by addition of 48.0g of TTE and stirring well. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Example 5
After mixing uniformly 17.5g of EMC and 8.9g of FEC, 15.6g of LiFSI was dissolved therein, followed by addition of 58.0g of HFME and stirring uniformly. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Example 6
17.5g of EMC and 8.9g of FEC were taken, mixed uniformly, and 15.6g of LiFSI was dissolved therein, followed by addition of 58.0g of BTFE and further stirring uniformly. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Example 7
The battery prepared in example 6 was taken and the charging voltage was increased to 4.43V upon the test. The cell in this comparative example was disassembled after the cycle test was completed and it was found that the positive electrode aluminum foil did not exhibit corrosion.
Comparative example 1
Mixing 16.0g EC, 54.0g EMC and 15.0g FEC, and mixing with LiPF615.0g was dissolved therein. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Taking a battery, discharging to 2.75V after 50 cycles are finished, stopping discharging, taking out the negative pole piece after disassembly, cleaning the negative pole piece for three times by using DMC, then drying in vacuum, and observing an SEI film formed on the surface of the pole piece under an electron microscope, wherein as shown in figure 2, the SEI film formed on the surface of the negative pole piece is very thick, loose and porous.
Comparative example 2
The battery prepared in comparative example 1 was taken and the charging voltage was increased to 4.43V upon the test. The battery in this comparative example was disassembled after the cycle test was completed, and it was found that the positive aluminum foil was more severely corroded.
Comparative example 3
41.5g of EMC and 21.2g of FEC were taken, and 37.3g of LiFSI was dissolved therein after mixing uniformly. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
After the cycle test is finished, the battery in the comparative example is disassembled in a full-charge state, and the phenomenon that the wettability of the electrolyte on a pole piece and a diaphragm is poor and lithium is separated from part of a negative electrode area is found.
Comparative example 4
26.2g of EMC was taken, 15.6g of LiFSI was then added, and after the lithium salt had dissolved sufficiently, 58.2g of TTE was added and stirred well. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Comparative example 5
After 15.6g of EMC and 4.0g of FEC were taken and mixed uniformly, 32.4g of LiFSI was dissolved therein, and then 48.0g of TTE was added thereto and stirred uniformly, and the resulting electrolyte became turbid, indicating that lithium salt was precipitated. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Comparative example 6
8.8g of EMC and 4.5g of FEC are taken, 7.9g of LiFSI is dissolved in the mixture after uniform mixing, then 78.8g of TTE is added and the mixture is stirred uniformly, and the obtained electrolyte is slightly turbid. And injecting the obtained electrolyte into the pure silicon cathode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
The electrolyte formulations, concentrations and test results of the above examples and comparative examples are summarized in table 1:
TABLE 1
The preparation method of the silicon oxide-graphite composite cathode lithium ion battery mainly comprises the following steps:
preparing a positive plate: the mass percentage of the mixed positive active substance, the conductive agent and the binding agent is 97.1:1.2:1.7, wherein the positive active substance is LiNi0.8Mn0.1Co0.1O2(NMC811), the specific preparation process is as follows: weighing an NMC811 positive electrode material, conductive carbon black and polyvinylidene fluoride (PVDF) binder powder in proportion into a charging bucket, premixing for 60min by using a double planetary mixer, adding N-methyl pyrrolidone (NMP) as a solvent, stirring for 90min at a high speed to obtain viscous positive electrode slurry, uniformly coating the viscous positive electrode slurry on an aluminum foil, drying and rolling, and punching a pole piece into small pieces with the size of 52 x 75 mm.
Preparing a negative plate: the mass percentage of the carbon-coated silicon oxide material, the artificial graphite, the conductive agent, the thickening agent and the binding agent is 12:81.2:0.3:2:4.5, and the preparation process comprises the following steps: weighing carbon-coated silica material, artificial graphite, single-walled carbon nanotube conductive agent and sodium carboxymethylcellulose (CMC) in proportion into a charging tank, premixing for 30min by using a double-planetary mixer, adding adhesives (50% Styrene Butadiene Rubber (SBR) aqueous emulsion and half of 10% polyacrylic acid aqueous solution), adding a proper amount of deionized water as a solvent, mechanically mixing to prepare viscous negative electrode slurry, uniformly coating the slurry on a copper foil, drying and rolling, and punching a pole piece into small pieces with the size of 53.5 x 76.5 mm.
Assembling the silicon-containing lithium ion battery: stacking the positive plate, the negative plate and the diaphragm prepared according to the process into a plate group according to a Z-shaped process, respectively performing pre-spot welding on positive and negative foil strips on the plate group on an ultrasonic spot welding machine, removing the length of redundant foil materials, respectively performing spot welding on an aluminum lug at the end of the positive aluminum strip, welding a nickel lug at the end point of the negative copper strip, pasting protective adhesive paper on the welded part of the lug, then packaging into an aluminum-plastic bag, performing processes such as top side sealing and the like to prepare the plate group, aging for 24 hours at 40 ℃, injecting electrolyte and packaging, performing clamping and pressing on the battery after aging for 48 hours at 40 ℃, then degassing, placing the battery in an aging box, performing capacity division (4.25V-2.75V) after aging for 48-72 hours, and then measuring the size, the weight and other performance tests.
Example 8
Weighing 10.20g PC, 4.10g EP, 11.30g PP, 2.70g FEC, 0.68g VEC and 0.34g PS in sequence, mixing well, adding 2.73g LiBF respectively4，8.19g LiFSI，12.29g LiPF612.29g of LiODFB, 1.23g of LiTFSI and 1.23g of LiBOB were dissolved therein, and 32.41g of BTTE was added thereto and stirred uniformly. And injecting the obtained electrolyte into a silicon oxide-graphite composite negative electrode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Example 9
13.30g of PC, 5.30g of EP, 14.60g of PP, 3.5g of FEC, 0.87g of VEC and 0.44g of PS are weighed in sequence, mixed uniformly and added with 1.00g of LiBF respectively4，3.00g LiFSI，4.50g LiPF64.50g of LiODFB, 0.45g of LiTFSI and 0.45g of LiBOB were dissolved therein, followed by addition of 48.00g of BTTE and further stirring to homogenize. And injecting the obtained electrolyte into a silicon oxide-graphite composite negative electrode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Example 10
13.30g of PC, 5.30g of EP, 14.60g of PP, 3.5g of FEC, 0.87g of VEC and 0.44g of PS are weighed in sequence, mixed uniformly and added with 1.00g of LiBF respectively4，3.00g LiFSI，4.50g LiPF64.50g of LiODFB, 0.45g of LiTFSI and 0.45g of LiBOB were dissolved therein, followed by addition of 48.00g of HFME and stirring to homogenize. And injecting the obtained electrolyte into a silicon oxide-graphite composite negative electrode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Example 11
13.30g of PC, 5.30g of EP, 14.60g of PP, 3.5g of FEC, 0.87g of VEC and 0.44g of PS are weighed in sequence, mixed uniformly and added with 1.00g of LiBF respectively4，3.00g LiFSI，4.50g LiPF64.50g of LiODFB, 0.45g of LiTFSI and 0.45g of LiBOB were dissolved therein, followed by addition of 48.00g of TMMP and further stirring to homogenize. Injecting the obtained electrolyte into a silicon oxide-graphite composite cathode lithium ion battery, and then carrying out follow-upBattery preparation and testing processes.
Example 12
13.30g of PC, 5.30g of EP, 14.60g of PP, 3.5g of FEC, 0.87g of VEC and 0.44g of PS are weighed in sequence, mixed uniformly and added with 1.00g of LiBF respectively4，3.00g LiFSI，4.50g LiPF64.50g of LiODFB, 0.45g of LiTFSI and 0.45g of LiBOB were dissolved therein, and then 24.00g of TTE and 24.00g of BTFE were added thereto and stirred uniformly. And injecting the obtained electrolyte into a silicon oxide-graphite composite negative electrode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
Comparative example 7
30.00g of PC, 12.00g of EP, 33.00g of PP, 8.00g of FEC, 2.00g of VEC and 1.00g of PS are weighed in sequence, evenly mixed and respectively added with 1.00g of LiBF4，3.00g LiFSI，4.50g LiPF64.50g of LiODFB, 0.45g of LiTFSI and 0.45g of LiBOB were dissolved therein and stirred uniformly. And injecting the obtained electrolyte into a silicon oxide-graphite composite negative electrode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
The cell in this comparative example was disassembled after the end of the cycle test and found that the aluminum foil of the positive electrode exhibited a slight corrosion phenomenon.
Comparative example 8
Weighing 15.20g PC, 6.06g EP, 16.70g PP, 4.00g FEC, 1.01g VEC and 0.51g PS in sequence, mixing well, adding 4.04g LiBF respectively4，12.12g LiFSI，18.18g LiPF618.18g of LiODFB, 1.82g of LiTFSI and 1.82g of LiBOB were dissolved therein and stirred uniformly. And injecting the obtained electrolyte into a silicon oxide-graphite composite negative electrode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
The battery in the comparative example is disassembled in a full-power state after the cycle test is finished, and the results show that the wettability of the electrolyte on the pole piece and the diaphragm is poor, lithium is embedded on the surface of the negative electrode unevenly, and a part of the negative electrode area is not golden yellow, which indicates that the area cannot be fully embedded with lithium due to no impregnation of the electrolyte, and lithium precipitation occurs in a part of the negative electrode area.
Comparative example 9
14.00g of PC, 5.58g of EP and 15.40g of PP are weighed in sequence and mixed evenly,1.05g of LiBF were added separately4，3.15g LiFSI，4.73g LiPF64.73g of LiODFB, 0.47g of LiTFSI and 0.47g of LiBOB were dissolved therein, and then 50.00g of BTFE was added thereto and stirred uniformly. And injecting the obtained electrolyte into a silicon oxide-graphite composite negative electrode lithium ion battery, and then carrying out subsequent battery preparation and test processes.
The electrolyte formulations, concentrations and test results of the above examples and comparative examples are summarized in table 2:
TABLE 2
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (5)
1. A silicon-containing high energy density lithium ion battery is characterized in that: the packaging material comprises a positive electrode, a silicon-containing negative electrode, fluorine-containing electrolyte, a diaphragm, a tab and a packaging material;
the silicon-containing negative electrode takes a silicon-based material as all or part of electrochemical active substances;
the electrolyte consists of lithium salt, a nonaqueous organic solvent capable of dissolving the lithium salt, SEI film forming additive and hydrofluoroether;
the solubility of lithium salt in the nonaqueous organic solvent capable of dissolving lithium salt is higher than 2 mol/L;
the solubility of lithium salt in said hydrofluoroether is less than 0.3 mol/L;
the nonaqueous organic solvent capable of dissolving the lithium salt is mutually soluble with the hydrofluoroether;
the nonaqueous organic solvent capable of dissolving the lithium salt is mutually soluble with the liquid SEI film forming additive, and can dissolve the solid SEI film forming additive;
the hydrofluoroether is selected from at least one of the following structural general formula (1):
wherein: r1 is selected from C1-C10 fluoroalkyl;
r2 is selected from C1-C10 alkyl or C1-C10 fluoroalkyl;
the molar concentration of the lithium salt in the whole fluorine-containing electrolyte is 0.7-4 mol/L;
in the electrolyte, the mass fraction of the nonaqueous organic solvent capable of dissolving lithium salt is 16-80%, the mass fraction of the SEI film-forming additive is 1-25%, and the mass fraction of the hydrofluoroether is 31.6-70%.
2. The silicon-containing high energy density lithium ion battery of claim 1, wherein: the molar concentration of the lithium salt in the mixture of the nonaqueous organic solvent in which the lithium salt is soluble and the SEI film-forming additive is 1 to 5 mol/L.
3. The silicon-containing high energy density lithium ion battery of claim 1, wherein: the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis (oxalato) borate, lithium trifluoro methyl sulfonate, lithium tris (trifluoromethylsulfonyl) methide, lithium bis (trifluoromethylsulfonyl) imide, lithium bis (fluorosulfonato) imide and lithium difluoro (oxalato) borate.
4. The silicon-containing high energy density lithium ion battery of claim 1, wherein: the non-aqueous organic solvent capable of dissolving the lithium salt is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylpropyl carbonate, dipropyl carbonate, methyl ethyl carbonate, gamma-butyrolactone, methyl formate, methyl acetate, ethyl propionate, propyl propionate and acetonitrile.
5. The silicon-containing high energy density lithium ion battery of claim 1, wherein: the SEI film forming additive is selected from one or more of vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, difluoroethylene carbonate, propylene sulfite, ethylene sulfite, dimethyl sulfite, diethyl sulfite, tris (2,2, 2-trifluoroethyl) phosphite, 1, 3-propylene sultone, dimethyl sulfoxide, methyl chloroformate, 1, 4-butane sultone, ethyl methanesulfonate, butyl methanesulfonate, bromo-butyrolactone, fluoroacetoxyethane, 1, 2-trifluoroacetoxyethane, anisole, N-dimethyl trifluoroacetamide and chloroethylene carbonate.
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| KR102565048B1 (en) * | 2018-03-08 | 2023-08-08 | 주식회사 아모그린텍 | Electrolyte for secondary battery, battery and flexible battery comprising the same |
| EP3944395A4 (en) * | 2019-07-22 | 2022-06-01 | LG Energy Solution, Ltd. | Lithium secondary battery |
| FR3100384B1 (en) * | 2019-08-29 | 2021-08-06 | Accumulateurs Fixes | COMPOSITION OF FLUORINE ELECTROLYTE FOR LITHIUM-ION ELECTROCHEMICAL ELEMENT |
| CN110649322A (en) * | 2019-09-03 | 2020-01-03 | 河南豫清新能源产业有限公司 | Method for manufacturing high-specific-energy lithium ion battery |
| CN110534807A (en) * | 2019-09-29 | 2019-12-03 | 河南省法恩莱特新能源科技有限公司 | A kind of LiNi0.5Mn1.5O4Positive lithium-ion battery electrolytes and preparation method |
| CN111276744A (en) * | 2020-02-12 | 2020-06-12 | 清华大学 | Local high-concentration lithium metal battery electrolyte containing anion receptor additive |
| CN111384450B (en) * | 2020-03-20 | 2021-05-11 | 广州明美新能源股份有限公司 | Liquid injection formation method of lithium ion battery |
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