CN109671974A - A kind of low temperature fast charge long-life high power dynamic lithium battery - Google Patents

A kind of low temperature fast charge long-life high power dynamic lithium battery Download PDF

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Publication number
CN109671974A
CN109671974A CN201811500517.1A CN201811500517A CN109671974A CN 109671974 A CN109671974 A CN 109671974A CN 201811500517 A CN201811500517 A CN 201811500517A CN 109671974 A CN109671974 A CN 109671974A
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CN
China
Prior art keywords
low temperature
fast charge
lithium battery
high power
power dynamic
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Pending
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CN201811500517.1A
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Chinese (zh)
Inventor
钱国珠
郑春龙
李菊香
刘涛
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JIANGSU TENPOWER LITHIUM CO Ltd
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JIANGSU TENPOWER LITHIUM CO Ltd
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Priority to CN201811500517.1A priority Critical patent/CN109671974A/en
Publication of CN109671974A publication Critical patent/CN109671974A/en
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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

Abstract

The invention discloses a kind of low temperature fast charge long-life high power dynamic lithium batteries, including anode, cathode, diaphragm and electrolyte, the anode material of lithium battery is selected from particle size range in the nickel-cobalt-manganese ternary active material of 1-10um, the negative electrode material selects the graphite material for being coated with 2~5% soft carbons, electrolyte solvent ratio is that EC:EMC:DMC is 1.5-2:0.5-1:7-8, and lithium salt content is 19~20%.The present invention significantly improves its performance in terms of high/low temperature and fast charge by improving to positive electrode, electrolyte solvent, lithium salt and reservoir quantity etc..

Description

A kind of low temperature fast charge long-life high power dynamic lithium battery
Technical field
The present invention relates to a kind of low temperature fast charge long-life high power dynamic lithium batteries, belong to technical field of lithium batteries.
Background technique
For other batteries, tool batteries are as Civil battery, it is necessary to adapt to environmental requirement, quick charge is moved Power foot, can just receive public favor, and battery can just go abroad, and move towards internationalization, the 18650-2.0Ah of our company production at present Battery existing defects on low temperature rapid charging performance, winter can not start, and can not accomplish the quick charge in half an hour, it is necessary to It is further improved in terms of low temperature fast charge, improves battery performance, better meet producer's requirement.
Summary of the invention
There is the dynamic of superperformance in terms of the technical problem to be solved by the invention is to provide a kind of high/low temperature and fast charge Power lithium battery.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of low temperature fast charge long-life high power dynamic lithium battery, including anode, cathode, diaphragm and electrolyte, it is described Anode material of lithium battery is selected from particle size range in the nickel-cobalt-manganese ternary active material of 1-10um, and the negative electrode material selection is coated with The graphite material of 2~5% soft carbons, electrolyte solvent ratio are that EC:EMC:DMC is 1.5-2:0.5-1:7-8, lithium salt content 19 ~20%.
Further, it is 2:1:7 that electrolyte solvent ratio, which is EC:EMC:DMC,.
Further, injecting electrolytic solution amount is 5.2-5.8g.
Further, injecting electrolytic solution amount is 5.4-5.6g.
Further, also added with one of EP, FEC, LiDFOB, LiPO2F2, TMSP, LiFSI in the electrolyte Or it is a variety of.
Further, by percentage to the quality, additive amount is EP 1-2%, FEC 2-7%, LiDFOB 0.5- respectively 1%, LiPO2F2 0.5-1%, TMSP 0.5-1%, LiFSI 0.5-1%.
Further, the lithium salts is LiPF6.
Advantageous effects of the invention:
(1) by being screened to positive electrode partial size, to improve the consistency of particle, thus reduce high temperature side reaction, Improve high-temperature behavior；
(2) soft carbon is coated by carrying out surface to negative electrode material, to promote rapid charging performance；
(3) by being investigated to electrolyte ratio, the preferred low electrolyte prescription of molten point out, so as to improve low temperature properties Energy；
(4) by carrying out gradient test to injecting electrolytic solution amount, suitable reservoir quantity is selected, can satisfy big multiplying power discharging Performance.
Detailed description of the invention
Fig. 1 is existing positive electrode particulate percentages size distribution；
Fig. 2 is positive electrode particulate percentages size distribution in embodiment；
Fig. 3 is bimodal distribution positive electrode SEM figure；
Fig. 4 is Unimodal Distribution positive electrode SEM figure；
Fig. 5 is mono-/bis-peak positive electrode preparation battery core EDS comparison diagram；
Fig. 6 is embodiment compared with comparative example negative electrode material EIS impedance spectrum；
Fig. 7 is embodiment battery EIS trace analysis corresponding with comparative example negative electrode material；
Fig. 8 is embodiment and comparative example discharge curve；
Fig. 9 is that embodiment and comparative example cycle performance compare；
Figure 10 is embodiment electrolyte and existing electrolyte agglomerates at -20 DEG C situation comparison diagram；
Figure 11 is electrolyte viscosity/conductivity comparing result at different temperatures；
Figure 12 is embodiment compared with comparative example discharge curve；
Figure 13 is the cycle performance comparison of different lithium salts；
Figure 14 is compared using the cycle performance of different reservoir quantities.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.Following embodiment is only used for clearly illustrating the present invention Technical solution, and not intended to limit the protection scope of the present invention.
The present invention is improved to existing lithium battery, to improve its performance in terms of low temperature fast charge.
Comparative example: former 18650-2.0 lithium battery uses 532 nickel-cobalt-manganese ternary materials for positive electrode, and graphite is cathode material Material, electrolyte organic solvent EC, EMC, DMC match as 2:2:6, LiPF6 lithium salt 12-14%.
Now improved from the following aspects
One, positive electrode partial size
From Fig. 1, original positive electrode granularity uniformity known to Fig. 3 is poor, predominantly bimodal distribution, wherein 1 μm of little particle of < Quantity is very more, and in the presoma sintering process of size particles, because reuniting, surface cladding unevenly causes small-particulate materials to exist Defect, relatively more active, side reaction is violent, by screening to material particle size, as shown in Fig. 2, positive electrode particle of the present invention < 1um little particle below is removed, primary particle size is distributed in 1-10um, as shown in figure 4, particle surface is smooth, spherical rule will Battery is made in size particles blending and the relatively uniform material of granularity, 60 degree of high temperature storages of full electric state is carried out, to bad after storage Battery core carries out EDS analysis, and detection Ni dissolves out ratio, as shown in figure 5, the Ni dissolution ratio of discovery Unimodal Distribution is smaller, and it is bimodal The Ni of distribution dissolves out large percentage, and storage is caused to be failed.
Two, negative electrode material coats
In lithium ion battery charging process, lithium ion is migrated from anode to cathode, and is embedded into the stratiform knot of graphite material In structure, concentration polarization and activation polarization can be generated in the process, and negative potential is caused to be lower than its actual stationary potential, with The increase of charging rate, polarization can be further aggravated, and side reaction aggravation causes negative terminal surface to form plated metallic lithium or dendrite, Cause safety issue and capacity problem.For soft carbon due to the presence of its undefined structure, interlamellar spacing is larger, so that lithium ion is more It is easy insertion, graphite surface is coated on by soft carbon material, the fast charge under the rapid charging performance even low temperature of battery can be improved Energy.
The present embodiment soft carbon covering amount 3%, using pole piece made of EIS testing example and comparative example material impedance with Diffusion is compared by XRD I002/I110 feature p-ratio and EIS data, verifies reliability and test full battery fast charge is followed Ring performance, for concrete outcome as shown in Fig. 5-Fig. 9 and table 1, being coated with the graphite-phase of soft carbon has that impedance is low, diffusivity than graphite Feature good, rapid charging performance is good
1 embodiment of table and comparative example negative electrode material OI value are tested
Three, electrolyte prescription optimizes
(1) by adjusting the proportion of in the mixed solvent different boiling solvent, high boiling solvent ratio is reduced, low boiling point is increased Solvent ratios, the molten point of Lai Gaishan mixed solvent, the present invention in adjustment ratio be 2:1:7.The results are shown in Figure 10, after improvement Electrolyte will not generate caking phenomenon at -20 DEG C, and there are caking phenomenons for comparative example electrolyte.
(2) add special solvent such as EP 1-2%, FEC 2-7%, LiDFOB 0.5-1%, LiPO2F2 0.5-1%, The additive that TMSP 0.5-1%, LiFSI 0.5-1% etc. improve SEI film promotes the cryogenic property of electrolyte；As a result such as Figure 11 Shown, compared with comparing electrolyte, under low temperature, the viscosity decline for implementing electrolyte after improvement is unobvious, and conductivity is relatively high, Illustrate that implement electrolyte has stronger cryogenic property at low temperature, full battery subtracts in -20 degrees Celsius of lower voltage dies after implementation Gently, discharge platform rises, as shown in figure 12.
(3) lithium salt is adjusted, and after lithium salt is promoted to 19-20% in the present invention, as a result as shown in figure 13, is implemented The big circulation performance of the battery of example electrolyte is substantially improved；
(4) reservoir quantity is adjusted, and by the gradient decline of electrolyte content, (6g to 5.2g) compares, the circulation of electrolyte content battery Performance gets a promotion, and the gas production of inside battery is controlled, it is possible to reduce the generation of side reaction, as a result as shown in figure 14.
Table 2 is using the finished battery performance parameter prepared after above-mentioned optimization
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations Also it should be regarded as protection scope of the present invention.

Claims (7)

1. a kind of low temperature fast charge long-life high power dynamic lithium battery, including anode, cathode, diaphragm and electrolyte, feature It is that the anode material of lithium battery is selected from particle size range in the nickel-cobalt-manganese ternary active material of 1-10um, the negative electrode material choosing With the graphite material for being coated with 2~5% soft carbons, electrolyte solvent ratio is that EC:EMC:DMC is 1.5-2:0.5-1:7-8, lithium salts Content is 19~20%.
2. a kind of low temperature fast charge long-life high power dynamic lithium battery according to claim 1, characterized in that electrolyte Solvent ratios are that EC:EMC:DMC is 2:1:7.
3. a kind of low temperature fast charge long-life high power dynamic lithium battery according to claim 1, characterized in that electrolyte Reservoir quantity is 5.2-5.8g.
4. a kind of low temperature fast charge long-life high power dynamic lithium battery according to claim 3, characterized in that electrolyte Reservoir quantity is 5.4-5.6g.
5. a kind of low temperature fast charge long-life high power dynamic lithium battery according to claim 1, characterized in that the electricity It solves in liquid also added with one of EP, FEC, LiDFOB, LiPO2F2, TMSP, LiFSI or a variety of.
6. a kind of low temperature fast charge long-life high power dynamic lithium battery according to claim 5, characterized in that with quality Percentages, additive amount are EP 1-2%, FEC 2-7%, LiDFOB 0.5-1%, LiPO2F2 0.5-1%, TMSP respectively 0.5-1%, LiFSI 0.5-1%.
7. a kind of low temperature fast charge long-life high power dynamic lithium battery according to claim 1, characterized in that the lithium Salt is LiPF6.
CN201811500517.1A 2018-12-10 2018-12-10 A kind of low temperature fast charge long-life high power dynamic lithium battery Pending CN109671974A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110911644A (en) * 2019-10-30 2020-03-24 深圳市卓能新能源股份有限公司 Lithium ion positive coating and lithium ion battery
CN110957476A (en) * 2019-10-30 2020-04-03 深圳市卓能新能源股份有限公司 High-rate lithium ion power battery and manufacturing method thereof
CN110957463A (en) * 2019-10-30 2020-04-03 深圳市卓能新能源股份有限公司 Positive pole piece, lithium ion battery and manufacturing method thereof
CN111048749A (en) * 2019-10-30 2020-04-21 深圳市卓能新能源股份有限公司 Negative pole piece, lithium ion battery and manufacturing method thereof

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CN106571463A (en) * 2016-11-10 2017-04-19 苏州大时代能源科技有限公司 Lithium ion battery and preparation method thereof
CN107482253A (en) * 2017-07-18 2017-12-15 东莞市迈科新能源有限公司 A kind of low-temperature lithium ion battery

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CN102208615A (en) * 2011-05-05 2011-10-05 钱承亮 Method for preparing carbon-carbon composite lithium ion battery cathode material
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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN110911644A (en) * 2019-10-30 2020-03-24 深圳市卓能新能源股份有限公司 Lithium ion positive coating and lithium ion battery
CN110957476A (en) * 2019-10-30 2020-04-03 深圳市卓能新能源股份有限公司 High-rate lithium ion power battery and manufacturing method thereof
CN110957463A (en) * 2019-10-30 2020-04-03 深圳市卓能新能源股份有限公司 Positive pole piece, lithium ion battery and manufacturing method thereof
CN111048749A (en) * 2019-10-30 2020-04-21 深圳市卓能新能源股份有限公司 Negative pole piece, lithium ion battery and manufacturing method thereof
CN111048749B (en) * 2019-10-30 2022-01-14 深圳市卓能新能源股份有限公司 Negative pole piece, lithium ion battery and manufacturing method thereof

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Application publication date: 20190423