CN112436190A - Lithium ion battery electrolyte and lithium ion battery thereof - Google Patents
Lithium ion battery electrolyte and lithium ion battery thereof Download PDFInfo
- Publication number
- CN112436190A CN112436190A CN201910787020.0A CN201910787020A CN112436190A CN 112436190 A CN112436190 A CN 112436190A CN 201910787020 A CN201910787020 A CN 201910787020A CN 112436190 A CN112436190 A CN 112436190A
- Authority
- CN
- China
- Prior art keywords
- lithium ion
- ion battery
- electrolyte
- lithium
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 66
- 239000003792 electrolyte Substances 0.000 title claims abstract description 40
- 239000000654 additive Substances 0.000 claims abstract description 21
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229910001290 LiPF6 Inorganic materials 0.000 claims abstract description 5
- 229910013188 LiBOB Inorganic materials 0.000 claims abstract description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 8
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical group O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 claims description 4
- 229920006255 plastic film Polymers 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- 239000011163 secondary particle Substances 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004880 explosion Methods 0.000 description 30
- 238000012360 testing method Methods 0.000 description 18
- 239000002904 solvent Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000003677 abuse test Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
-
- 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
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery electrolyte and a lithium ion battery thereof, wherein the electrolyte consists of an organic solvent, a lithium salt, a film forming additive and a high temperature additive, the sum of the components is 100%, the organic solvent is a ternary system of EC: EMC: DEC = 35: 30: 35, and the lithium ion battery electrolyte has high ionic conductivity. The lithium salt (11.40% -12.50%) is LiPF6Or LiPF6The LiBOB mixed with the lithium ion battery (0-0.4%) can meet the requirement of the lithium ion battery for 0.5C circulation for 400 weeks and control the cost. The film forming additive VC is beneficial to forming a good SEI film, and improves the multiplying power, storage, low-temperature discharge and high-temperature discharge performance of the battery. The high-temperature additive PS can effectively improve the high-temperature storage performance of the battery. The lithium ion battery obtained by the invention has good safety performance, capacity retention rate of more than 80 percent at 0.5C cycle of 400 weeks, and easy mass production。
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte and a lithium ion battery thereof.
Background
The electrolyte is an important factor influencing the performance of the lithium ion battery, is called as the blood of the lithium ion battery, and plays a role in conducting ions between the positive electrode and the negative electrode in the lithium ion battery. The organic solvent of the electrolyte is generally a mixture of a high dielectric constant solvent and a low viscosity solvent, and the common organic solvent is a binary or ternary body, such as ethylene carbonate + dimethyl carbonate, ethylene carbonate + diethyl carbonate, ethylene carbonate + dimethyl carbonate + methylethyl carbonate, ethylene carbonate + methylethyl carbonate + diethyl carbonate, and the like, which is determined according to the use conditions, and the safety performance of the common ternary system electrolyte is higher than that of the binary body. Lithium salts in the electrolyte include lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium dioxalate borate and the like, but lithium hexafluorophosphate is a main electrolyte adopted by commercial lithium ion batteries in view of cost, safety and the like. The additive in the electrolyte can improve the electrochemical performance of an electrolyte system, if vinylene carbonate is added, the additive can participate in forming an SEI protective film, the obtained film has good ion permeability and good electronic insulation, lithium ions can enter and exit from a negative electrode in the charging and discharging process, but electrons on the negative electrode cannot contact with solvent molecules, the multiplying power performance is improved, the performances in various aspects such as storage, low-temperature discharge, high-temperature discharge and the like are also improved, and if a certain amount of 1, 3-propane sultone is added, the high-temperature storage performance of the battery can be effectively improved. The commonly used lithium ion battery electrolyte additive is different in types and amounts according to different requirements, and of course, the price of the additive is quite expensive, so that the selection is needed preferentially.
Lithium ion batteries have been widely used in electronic products such as smart phones and tablet computers, and rapid development of the mobile power supply market is promoted along with the contradiction between large screen, multiple applications, ultra-thinning and the electric quantity of the lithium ion batteries of the smart phones. The competition is quite intense due to the correspondingly low market threshold of mobile power supplies. And the mobile power supply product with absolute price advantage, high capacity, long service life and good safety performance is more popular. The price, capacity, service life and safety performance of the mobile power supply are mainly determined by the lithium ion battery, so that the lithium ion battery for the mobile power supply is required to have the advantages of low price, high capacity, long service life and good safety performance. Since the purchase price of several major main materials of lithium ion batteries such as anode materials, cathode materials, diaphragms, aluminum plastic films and tabs on the market is basically opened, the development of a lithium ion battery electrolyte which can meet the related performance requirements of the lithium ion battery and has absolute price advantage becomes an urgent need of manufacturers of various large lithium ion batteries. The lithium ion battery electrolyte can meet the related performance requirements of the lithium ion battery, and the lithium ion battery prepared by the invention has good safety and low cost, and the capacity retention rate of 400 weeks can reach more than 80 percent by 0.5C circulation.
Disclosure of Invention
The invention mainly aims to provide a lithium ion battery electrolyte with low cost, good safety performance and good cycle performance and a lithium ion battery thereof, and the invention realizes the aim, and adopts the following technical scheme:
the electrolyte of the lithium ion battery comprises an organic solvent, a lithium salt, a film-forming additive and a high-temperature additive, wherein the organic solvent is 82-86%, the lithium salt is 11.4-12.5%, the film-forming additive is 1.0-2.0%, the high-temperature additive is 2.0-3.0%, the sum of the components is 100%, and the molar concentration of the lithium salt is 0.90-0.99 mol/L.
The organic solvent is a ternary organic solvent system formed by mixing ethylene carbonate EC: methyl ethyl carbonate EMC: diethyl carbonate DEC according to a ratio of 35: 30: 35.
The lithium salt is monomer lithium hexafluorophosphate LiPF6Or lithium hexafluorophosphate is mixed with (0% -0.4%) lithium LiBOB.
The film forming additive is vinylene carbonate VC.
The high-temperature additive is 1, 3-propane sultone PS.
The lithium ion battery using the electrolyte disclosed by the invention comprises a positive electrode, a negative electrode, a diaphragm, an aluminum plastic film, the electrolyte and a lug.
The positive electrode is one or two of nickel cobalt lithium manganate and lithium manganate.
The negative electrode is artificial graphite of primary particles, or secondary particles, or a mixture of the primary particles and the secondary particles.
The electrolyte is 4.2V system electrolyte, and the working cut-off voltage of the lithium ion battery is 4.2V.
The invention has the beneficial effects that: compared with the common lithium ion battery electrolyte with the lithium salt molar concentration of 1.0-1.2 mol/L, the lithium ion battery electrolyte and the lithium ion battery thereof with low cost, good safety performance and good cycle performance can be obtained by using the low lithium salt with the molar concentration of 0.90-0.99 mol/L under a specific solvent system and a specific film forming additive and a high-temperature additive, and the capacity retention rate of 400 weeks can reach more than 80% through 0.5C cycle; the lithium ion battery electrolyte obtained by the invention has simple components and easily controlled cost.
Detailed Description
In order that the invention may be clearly and clearly understood, the invention will now be further described by way of specific embodiments and proportions:
firstly, preparing an electrolyte:
mixing ethylene carbonate EC, ethyl methyl carbonate EMC, diethyl carbonate DEC in a glove box (moisture content < 5ppm, oxygen content < 1ppm) filled with argon gas at a volume ratio of 35: 30: 35 to obtain an organic mixed solvent. Then mixing the organic mixed solvent and lithium hexafluorophosphate LiPF6And mixing lithium bis (oxalato) borate LiBOB, vinylene carbonate VC and 1, 3-propane sultone PS according to a ratio of 85.6: 11.0: 0.4: 1.0: 2.0% so that the sum of the total amount of the organic solvent, the lithium salt, the vinylene carbonate and the 1, 3-propane sultone is 100%, and the molar concentration of the lithium salt is 0.9mol/L, thereby obtaining the lithium ion battery electrolyte of the embodiment 1.
The electrolyte preparation methods of examples 2 to 6 were the same as in example 1 except that the specific proportions of the respective components in the electrolyte were different.
Secondly, preparing the positive plate:
fully stirring and uniformly mixing active substance nickel cobalt lithium manganate, carbon nano tube slurry CNT and binder polyvinylidene fluoride PVDF in an N-methyl pyrrolidone solvent system according to the mass ratio of 98.6: 0.4: 1.0 to prepare anode slurry, coating the anode slurry on an anode current collector aluminum foil with the thickness of 14um, and rolling, splitting and spot-welding a tab to prepare an anode piece.
Thirdly, preparing the negative plate:
and (2) fully stirring and uniformly mixing the negative active material artificial graphite, the conductive carbon black Super P, the thickening agent sodium carboxymethylcellulose CMC and the styrene butadiene rubber SBR in a deionized water solvent system according to a mass ratio of 95: 1.1: 1.6: 2.3 to prepare a negative slurry, coating the negative slurry on a negative current collector copper foil with the thickness of 7 mu m, and rolling, slitting and spot-welding a lug to prepare a negative pole piece.
Fourthly, preparing the lithium ion battery:
winding the nickel cobalt lithium manganate positive pole piece, the graphite negative pole piece and the diaphragm, wrapping an aluminum plastic film, baking at 80 ℃ in vacuum to remove water, injecting the electrolyte, sealing, standing, forming by a fixture at 50 ℃, exhausting air, sealing again, grading and shaping to prepare the soft package battery.
In the above-described battery production process, the contents of the respective components used in the electrolyte solution selected for each battery are shown in table 1, and the contents of the respective components are mass percentages calculated based on the total mass of the electrolyte solution being 100%.
And (3) testing the cycle performance of the lithium ion battery, namely testing the cycle performance of the lithium ion battery in the embodiment 1-6. The lithium ion battery is charged to 4.2V at a constant current of 0.5C rate at 25 ℃, then charged to a cut-off current of 0.01C at a constant voltage of 4.2V, kept stand for 5 minutes, and then discharged to 3.0V at a constant current of 0.5C rate, wherein the discharge capacity is the first discharge capacity of the lithium ion battery, and then the charge-discharge cycle process is carried out for 400 times according to the method.
Capacity retention (%) after 400 cycles of the lithium ion battery (= (discharge capacity at 400 cycles/first discharge capacity) × 100%. The test results are shown in table 1, and the test results show that the capacity retention rate is far more than 80% after 0.5C circulation for 400 weeks, and the market demand of the mobile power supply can be met.
The safety performance of the lithium ion battery is tested, and the lithium ion battery in the embodiment 1-6 is subjected to the following safety performance test according to the test standard in GB 31241-2013:
1. and (3) testing the normal-temperature short circuit, namely charging the battery to be fully charged at 4.2V at constant current and constant voltage with 0.5C rate, placing the battery in an environment with the temperature of 20 +/-5 ℃, placing the battery for 30min after the surface temperature of the battery reaches 20 +/-5 ℃, connecting a lead with the internal resistance of 80 +/-20 m omega to the positive and negative ends of the battery for testing, and stopping the test when the surface temperature of the battery is reduced to be 20 percent lower than the peak value. And (5) judging the standard, wherein the battery is not ignited and not exploded, and the highest temperature of the surface of the battery is not more than 150 ℃. The test results are shown in Table 2.
2. And (3) high-temperature external short circuit test, namely, after the battery is fully charged to 4.2V at constant current and constant voltage with 0.5C multiplying power, placing the battery in an environment with the temperature of 55 +/-5 ℃, placing the battery for 30min after the surface temperature of the battery reaches 55 +/-5 ℃, connecting a lead with the internal resistance of 80 +/-20 m omega to the positive and negative ends of the battery for test, and stopping the test when the surface temperature of the battery is reduced to 20 percent lower than the peak value. And (5) judging the standard, wherein the battery is not ignited and not exploded, and the highest temperature of the surface of the battery is not more than 150 ℃. The test results are shown in Table 2.
3. The overcharge test was carried out by discharging the cell at a constant current of 0.5C rate to 3.0V in an environment of 25C, charging the cell at a constant current of 3C rate to 4.6V, and then charging the cell at a constant voltage of 4.6V, and the test was terminated when the cell temperature dropped to about 20% below the peak value. And (5) judging the standard that the battery does not catch fire or explode. The test results are shown in Table 2.
4. And (4) forced discharge test, wherein the battery is subjected to constant current discharge at 0.5C rate to 3.0V in an environment at 25 ℃, and then is subjected to reverse charge at 1C rate for 90 min. And (5) judging the standard that the battery does not catch fire or explode. The test results are shown in Table 2.
5. And (3) performing thermal abuse test, namely charging the battery to be full of 4.2V at constant current and constant voltage with 0.5C multiplying power, putting the battery into an experimental box, heating the experimental box at the temperature rise rate of (5 +/-2) DEG C/min, and keeping the temperature constant for 30min when the temperature in the box reaches 130 +/-2 ℃. And (5) judging the standard that the battery does not catch fire or explode. The test results are shown in Table 2.
Table 1:
table 2:
| examples | Short circuit at normal temperature | High temperature short circuit | Overcharge | Forced discharge | Heat abuse |
| Example 1 | The highest temperature of no fire and no explosion is 120.2 DEG C | No fire and explosion, and a maximum temperature of 130.5 DEG C | No fire and explosion, and the highest temperature of 82.6 DEG C | Without ignition and explosion | Without ignition and explosion |
| Example 2 | The highest temperature of no fire and no explosion is 118.3 DEG C | No fire and explosion, the highest temperature is 127.9 DEG C | No fire and explosion, and the highest temperature of 80.4 DEG C | Without ignition and explosion | Without ignition and explosion |
| Example 3 | The highest temperature of no fire and no explosion is 122.6 DEG C | No fire and explosion, the highest temperature is 126.4 DEG C | No fire and explosion, the highest temperature is 79.5 DEG C | Without ignition and explosion | Without ignition and explosion |
| Example 4 | The highest temperature of no fire and no explosion is 112.5 DEG C | No fire and explosion, and maximum temperature of 125.3 deg.C | No fire and explosion, and the highest temperature of 78.2 DEG C | Without ignition and explosion | Without ignition and explosion |
| Example 5 | The highest temperature of non-ignition and non-explosion is 114.2 DEG C | No fire and explosion, the highest temperature is 127.5 DEG C | No fire and explosion, the highest temperature is 79.8 DEG C | Without ignition and explosion | Without ignition and explosion |
| Example 6 | The highest temperature of no fire and no explosion is 110.1 DEG C | No fire and explosion, and maximum temperature of 125.7 deg.C | No fire and explosion, the highest temperature is 77.9 DEG C | Without ignition and explosion | Without ignition and explosion |
The results in table 2 show that the lithium ion battery safety performance tests all passed.
Compared with the common lithium ion battery electrolyte with the lithium salt molar concentration of 1.0-1.2 mol/L, the lithium ion battery electrolyte and the lithium ion battery thereof with low cost, good safety performance and good cycle performance can be obtained by using the low lithium salt with the molar concentration of 0.90-0.99 mol/L under a specific solvent system and a specific film forming additive and a high-temperature additive, and the capacity retention rate of 400 weeks can reach more than 80% through 0.5C cycle; the lithium ion battery electrolyte obtained by the invention has simple components and easily controlled cost.
The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any person skilled in the art can easily conceive of changes or substitutions without departing from the concept of the present application, and all of them are included in the protection scope of the present invention.
Claims (9)
1. The electrolyte of the lithium ion battery is characterized by comprising organic solvent, lithium salt, a film forming additive, a high-temperature additive (82-86%), 11.4-12.5%), 1.0-2.0%: (2.0% -3.0%), the sum of the components is 100%, and the molar concentration of the lithium salt is 0.90-0.99 mol/L.
2. The lithium ion battery electrolyte of claim 1, wherein the organic solvent is Ethylene Carbonate (EC): ethyl methyl carbonate EMC: diethyl carbonate DEC is mixed according to the proportion of 35: 30: 35 to form a ternary organic solvent system.
3. The lithium ion battery electrolyte of claim 1, wherein the lithium salt is monomeric lithium hexafluorophosphate LiPF6Or lithium hexafluorophosphate is mixed with (0% -0.4%) lithium LiBOB.
4. The lithium ion battery electrolyte of claim 1, wherein the film forming additive is Vinylene Carbonate (VC).
5. The lithium ion battery electrolyte of claim 1, wherein the high temperature additive is 1, 3-propane sultone PS.
6. A lithium ion battery containing the lithium ion electrolyte solution of any one of claims 1 to 5, wherein the lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm, an aluminum plastic film, an electrolyte solution and a tab.
7. The lithium ion battery according to claim 6, wherein the positive electrode is one or both of nickel cobalt lithium manganate and lithium manganate.
8. The lithium ion battery according to claim 6, wherein the negative electrode is artificial graphite in which primary particles, secondary particles, or a mixture of primary particles and secondary particles.
9. The lithium ion battery electrolyte and the lithium ion battery thereof according to claims 1 to 8, wherein the electrolyte is a 4.2V system electrolyte, and the lithium ion battery has an operating cut-off voltage of 4.2V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910787020.0A CN112436190A (en) | 2019-08-25 | 2019-08-25 | Lithium ion battery electrolyte and lithium ion battery thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910787020.0A CN112436190A (en) | 2019-08-25 | 2019-08-25 | Lithium ion battery electrolyte and lithium ion battery thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112436190A true CN112436190A (en) | 2021-03-02 |
Family
ID=74689877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910787020.0A Pending CN112436190A (en) | 2019-08-25 | 2019-08-25 | Lithium ion battery electrolyte and lithium ion battery thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112436190A (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101093901A (en) * | 2007-08-14 | 2007-12-26 | 深圳市海盈科技有限公司 | Constituents of electrolyte of lithium ion battery possessing function of guarding against over charge, and gaseous distention |
| US20110064998A1 (en) * | 2008-03-13 | 2011-03-17 | Ube Industries, Ltd. | Non-aqueous electrolyte for a lithium battery, lithium battery wherein said electrolyte is used, and hydroxy-acid derivative for use in said electrolyte |
| CN103354297A (en) * | 2013-06-21 | 2013-10-16 | 珠海市赛纬电子材料有限公司 | Non-water electrolyte of high voltage lithium ion battery and preparation method thereof |
| CN103384017A (en) * | 2013-07-04 | 2013-11-06 | 珠海市赛纬电子材料有限公司 | Non-aqueous electrolyte of high-voltage lithium ion batteries |
| CN103715458A (en) * | 2013-10-23 | 2014-04-09 | 江西优锂新材股份有限公司 | Preparation method of electrolyte used for lithium manganate power battery at high temperature |
| US20160013469A1 (en) * | 2014-07-11 | 2016-01-14 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and electronic device including the same |
| CN106785037A (en) * | 2016-12-26 | 2017-05-31 | 河南华瑞高新材料科技股份有限公司 | A kind of lithium-ion battery electrolytes for ternary material battery |
-
2019
- 2019-08-25 CN CN201910787020.0A patent/CN112436190A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101093901A (en) * | 2007-08-14 | 2007-12-26 | 深圳市海盈科技有限公司 | Constituents of electrolyte of lithium ion battery possessing function of guarding against over charge, and gaseous distention |
| US20110064998A1 (en) * | 2008-03-13 | 2011-03-17 | Ube Industries, Ltd. | Non-aqueous electrolyte for a lithium battery, lithium battery wherein said electrolyte is used, and hydroxy-acid derivative for use in said electrolyte |
| CN103354297A (en) * | 2013-06-21 | 2013-10-16 | 珠海市赛纬电子材料有限公司 | Non-water electrolyte of high voltage lithium ion battery and preparation method thereof |
| CN103384017A (en) * | 2013-07-04 | 2013-11-06 | 珠海市赛纬电子材料有限公司 | Non-aqueous electrolyte of high-voltage lithium ion batteries |
| CN103715458A (en) * | 2013-10-23 | 2014-04-09 | 江西优锂新材股份有限公司 | Preparation method of electrolyte used for lithium manganate power battery at high temperature |
| US20160013469A1 (en) * | 2014-07-11 | 2016-01-14 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and electronic device including the same |
| CN106785037A (en) * | 2016-12-26 | 2017-05-31 | 河南华瑞高新材料科技股份有限公司 | A kind of lithium-ion battery electrolytes for ternary material battery |
Non-Patent Citations (1)
| Title |
|---|
| 史鹏飞主编: "《化学电源工艺学》", 31 March 2006, 哈尔滨：哈尔滨工业大学出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102479973B (en) | Silicon cathode lithium ion battery | |
| CN111628218A (en) | A kind of lithium ion battery and preparation method thereof | |
| CN114024035B (en) | Battery with a battery cell | |
| CN102738511B (en) | Lithium ion battery and electrolyte thereof | |
| CN105098244A (en) | Electrolyte and lithium ion battery comprising same | |
| CN114976249B (en) | Electrolyte and sodium ion battery | |
| CN103346350A (en) | Electrolyte for improving performance of lithium ion battery and battery | |
| CN110931871A (en) | High-temperature-resistant electrolyte adaptive to silicon-carbon negative electrode material for lithium ion battery | |
| CN115911567B (en) | A type of battery | |
| CN116666789A (en) | Negative pressure formation method of lithium manganese iron phosphate battery and battery using same | |
| CN112687956A (en) | Non-aqueous electrolyte of lithium battery and lithium ion battery based on same | |
| CN110994029A (en) | Sulfone-based high-voltage electrolyte containing triphenylphosphine additives for lithium ion battery | |
| CN109119599B (en) | A kind of secondary battery and preparation method thereof | |
| CN103326064B (en) | A kind of electrolyte of safe lithium ion battery | |
| CN114094187A (en) | Non-aqueous electrolyte and battery comprising same | |
| CN111755745A (en) | A kind of lithium-sulfur battery electrolyte and injection method thereof | |
| CN105576291B (en) | A kind of high-voltage lithium ion battery electrolyte and lithium ion battery | |
| CN116435592A (en) | High-voltage ether gel electrolyte and preparation method and application thereof | |
| CN110808413A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| CN114024029A (en) | Non-aqueous electrolyte and battery comprising same | |
| CN117276671B (en) | Lithium ion battery electrolyte and preparation method thereof | |
| CN112713308A (en) | Non-aqueous electrolyte and lithium ion battery based on same | |
| CN107946643B (en) | High-performance lithium battery electrolyte | |
| CN118336112A (en) | Thermally responsive safety additive, electrolyte composition, electrolyte and preparation method thereof, and battery | |
| CN111416157B (en) | Preparation method of ternary lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210302 |
|
| RJ01 | Rejection of invention patent application after publication |