CN105336979A - Ternary lithium battery and preparing method thereof - Google Patents
Ternary lithium battery and preparing method thereof Download PDFInfo
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- CN105336979A CN105336979A CN201510883392.5A CN201510883392A CN105336979A CN 105336979 A CN105336979 A CN 105336979A CN 201510883392 A CN201510883392 A CN 201510883392A CN 105336979 A CN105336979 A CN 105336979A
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- lithium battery
- fire retardant
- ternary lithium
- retardant
- pvdf
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/058—Construction or manufacture
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a ternary lithium battery. The positive electrode of the battery is prepared from LiNixCoyMn1-x-yO2, conductive carbon black, PVDF and fire retardant. The fire retardant is prepared from at least one of phosphorus-based flame retardant, halogen-based flame retardant and composite flame retardant. A preparing method of the ternary lithium battery comprises the following steps that LiNixCoyMn1-x-yO2, conductive carbon black, PVDF and the fire retardant are weighed according to the mass ratio, and conductive carbon black, PVDF and the fire retardant are dissolved in an N-methyl pyrrolidone solution and stirred to be uniform; LiNixCoyMn1-x-yO2 is added into the solution, and pulping is carried out to obtain pulp; aluminum foil is evenly coated with the pulp, dried and sliced, and a positive electrode plate is obtained. The ternary lithium battery is prepared from the prepared positive electrode plate, a negative electrode plate, a diaphragm and an electrolyte. According to the ternary lithium battery, the fire retardant is added in the pulping process of the positive electrode, and the adverse impact on electrochemical performance is smaller compared with the mode that fire retardant is directly added into an electrolyte; the safety of the battery can be improved, and incomplete capacity play caused by poor compatibility of the fire retardant and the negative electrode can be avoided.
Description
Technical field
The invention belongs to field of lithium ion battery, particularly relate to a kind of ternary lithium battery and preparation method thereof.
Background technology
Ternary lithium battery refers to that positive electrode uses the lithium battery of lithium nickel-cobalt-manganese ternary positive electrode material.The safety problem of ternary lithium battery is a large bottleneck of current practical application, when high rate charge-discharge, various electrochemical reaction occurs inside battery causes the gentle pressure holding of internal temperature of battery height of continuing rising thus causes battery very easily thermal runaway, even causes burning and the blast of battery.The method of current report adds each based flame retardant in the electrolytic solution, and due to electrolyte meeting and cathode contact, and the compatibility of most of fire retardant and negative pole is poor, and therefore this feed postition can affect the performance of battery cathode capacity.
Summary of the invention
Technical problem to be solved by this invention accomplishes the performance not affecting battery cathode capacity while being to improve ternary lithium battery security performance.
For solving the problems of the technologies described above, the invention provides a kind of ternary lithium battery, comprise a positive plate, a negative plate, a barrier film and electrolyte, the composition of described positive plate comprises LiNi
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant mass ratio be: 85%-97%:1%-5%:1%-10%:2%-10%.
Further, described LiNi
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant mass ratio be: 92%:1.5%:1.5%:5%.
Further, described fire retardant comprises at least one in phosphorus flame retardant, halogenated flame retardant or composite flame-retardant agent.
Further, described phosphorus flame retardant comprises alkyl phosphate, fluorinated phosphate ester and phosphonitrile compounds; Described halogenated flame comprises fluoric cyclic carbonate, fluoro linear carbonate and alkyl-perfluoroalkyl ether; Described composite flame-retardant agent comprises phosphorus-nitrogen compound or halophosphoric acid ester complexes.
Further, described fire retardant is tetrabromobisphenol A and triphenyl phosphate composite flame-retardant agent.
For solving the problems of the technologies described above, present invention also offers a kind of preparation method of ternary lithium battery, comprising the following steps:
(1) LiNi is weighed respectively in mass ratio
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant, conductive black, PVDF and fire retardant are dissolved in 1-METHYLPYRROLIDONE solution, stir;
(2) in solution, LiNi is added
xco
ymn
1-x-yo
2, pull an oar, obtained slurry;
(3) slurry is evenly coated on aluminium foil, carries out drying, rod pressure, cut obtained positive plate;
(4) ternary lithium battery prepared by positive plate, negative plate, barrier film and electrolyte obtained by utilization;
Wherein, 0<x<1,0<y<1,0<x+y<1;
Described LiNi
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant mass ratio be: 85%-97%:1%-5%:1%-10%:2%-10%.
Further, described LiNi
xco
ymn
1-x-yo
2, conductive black and PVDF mass ratio be: 92%:1.5%:1.5%:5%.
Further, described fire retardant comprises at least one in phosphorus flame retardant or halogenated flame retardant.
Further, described phosphorus flame retardant comprises alkyl phosphate, fluorinated phosphate ester and phosphonitrile compounds; Described halogenated flame comprises fluoric cyclic carbonate, fluoro linear carbonate and alkyl-perfluoroalkyl ether; Described composite flame-retardant agent comprises phosphorus-nitrogen compound or halophosphoric acid ester complexes.
Further, described fire retardant is tetrabromobisphenol A and triphenyl phosphate mixture.
The present invention compared with prior art, beneficial effect is: a kind of ternary lithium battery provided by the invention and preparation method thereof, add fire retardant in anode pulping process, this is a kind of feed postition of new fire retardant, compare the negative effect of mode to the chemical property of ternary lithium battery directly added in the electrolytic solution less, because the compatibility of most of fire retardant and negative pole is poor, and is directly added in positive electrode, the Exposure of fire retardant and negative pole can be reduced.Both can improve the fail safe of battery, and can avoid again being played not exclusively by the poor capacity caused of compatibility of fire retardant and negative pole.Ternary lithium battery preparation method of the present invention, simple to operate, be convenient to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is provide in the embodiment of the present invention 25 DEG C and adds cycle performance of battery contrast before and after fire retardants.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Phosphorus flame retardant becomes gas phase when being heated, then decompose and produce phosphorus free radical, phosphorus free radical has the ability of catching hydroperoxyl radical in electrolyte system, and the chain tra nsfer of hydrocarbon combustion reaction because the shortage of hydroperoxyl radical is inhibited, and then stops combustion reaction.As triphenyl phosphate, gas phase can be become when triphenyl phosphate is heated, then decompose and produce P (phosphorus free radical), P has the ability of catching H in electrolyte system (hydroperoxyl radical), the chain tra nsfer of hydrocarbon combustion reaction because the shortage of H is inhibited, and then stops combustion reaction.
The fire retardant mechanism of halogenated flame mainly contains two aspects: first, and the decomposition temperature of C-X key is close with the heat decomposition temperature of material, and when the material is heated, fire retardant can absorption portion heat, reduces the temperature of material; Secondly, X can be combined with free radical H and HO that burning chain reaction generates, and stops burning to proceed.As tetrabromobisphenol A, when heated, first the decomposition temperature of C-Br key is close with the heat decomposition temperature of material, and when the material is heated, fire retardant can absorption portion heat, reduces the temperature of material; Secondly, free radical H and HO that Br can generate with chain reaction is combined, and stops the chain reaction of burning.
Prepare ternary lithium battery according to technical solution of the present invention, step is as follows:
(1) by LiNi
xco
ymn
1-x-yo
2, conductive black and PVDF mass ratio be: 5%-97%:1%-5%:1%-10%:2%-10% weighs LiNi respectively
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant (at least one in phosphorus flame retardant, halogenated flame retardant or composite flame-retardant agent), conductive black, PVDF and fire retardant are dissolved in 1-METHYLPYRROLIDONE solution, stir;
(2) in solution, LiNi is added
xco
ymn
1-x-yo
2, pull an oar, obtained slurry;
(3) slurry is evenly coated on aluminium foil, carries out drying, rod pressure, to cut, obtained positive plate;
(4) utilize obtained by positive plate, negative plate, (material can be PP (polypropylene) to barrier film, any one in the ceramic diaphragm of PE (polyethylene), PP/PE/PP tri-layers of barrier film or covering aluminum oxide coating) and electrolyte prepare ternary lithium battery;
Wherein, 0<x<1,0<y<1,0<x+y<1.
The ternary battery of described preparation is carried out pin prick test respectively, short circuit, overcharge, cross put test and 25 DEG C add cycle performance of battery contrast before and after fire retardants, prove that the present invention achieves technique effect.
Embodiment
Using 1-METHYLPYRROLIDONE to dissolve mass ratio is the PVDF of 1.5% and the conductive black of 1.5%, add simultaneously mass ratio be respectively 4% and 1% tetrabromobisphenol A and triphenyl phosphate as flame-retardant additive, be stirred to evenly, then add the LiNi that mass ratio is 92%
xco
ymn
1-x-yo
2tertiary cathode material (nickel, cobalt, manganese) is pulled an oar.Be coated on powder on anode pole piece and additive is evenly distributed, at 85 DEG C after coating, 8h condition is dried.Graphite, conductive black, aqueous adhesive are made into cathode size in mass ratio at 95.0: 1.5: 3.5, are evenly coated on Copper Foil, oven dry, rod pressure, cut obtained negative plate.Use ceramic diaphragm during positive/negative plate winding, enter shell final vacuum 85 DEG C and dry fluid injection after 7 days, select ternary battery electrolyte, complete other preparation processes according to method general in industry.
The ternary battery of described preparation and the ternary lithium battery not adding fire retardant carried out pin prick test and short circuit respectively, overcharges, cross and put test, result is: explosion phenomenon on fire occurs in the battery acupuncture experiment not adding fire retardant, short circuit, overcharges and crosses and put measured temperature in test and be respectively 63.2 DEG C, 51.3 DEG C and 31.8 DEG C; Add the battery after fire retardant not on firely not explode in acupuncture experiment, in short circuit, overcharge and cross and put measured temperature in test and be reduced to 55.2 DEG C, 45.1 DEG C and 29.6 DEG C respectively.The visible fire retardant that adds can reduce battery short circuit, overcharges, cross temperature rise when putting, improves the fail safe of lithium battery.
The ternary battery of described preparation is carried out 25 DEG C and add cycle performance of battery contrast before and after fire retardant, undertaken by three-step approach with CT-3008-15V20A-204 high accuracy battery Performance Test System: with 0.025C constant current charge 120min, turn 0.05C constant current charge 120min, last 0.15C constant current charge 240min.Preliminary filling only has electric current to arrange, and does not have voltage to arrange, and protection upper voltage limit is 4.20V.Result as shown in fig. 1, add before and after fire retardant, the capacity first of battery is respectively 4297.2mAh (MAH) and 4350.5mAh, after 260 weeks, capability retention is respectively 95.26% and 93.27%, visible, in anode sizing agent, add fire retardant on cycle performance of battery impact not quite.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a ternary lithium battery, comprise a positive plate, a negative plate, a barrier film and electrolyte, it is characterized in that, the composition of described positive plate comprises LiNi
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant;
Wherein 0<x<1,0<y<1,0<x+y<1;
Described LiNi
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant mass ratio be: 85%-97%:1%-5%:1%-10%:2%-10%.
2. ternary lithium battery as claimed in claim 1, is characterized in that, described LiNi
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant mass ratio be: 92%:1.5%:1.5%:5%.
3. ternary lithium battery as claimed in claim 1, it is characterized in that, described fire retardant comprises at least one in phosphorus flame retardant, halogenated flame retardant or composite flame-retardant agent.
4. ternary lithium battery as claimed in claim 3, it is characterized in that, described phosphorus flame retardant comprises alkyl phosphate, fluorinated phosphate ester and phosphonitrile compounds; Described halogenated flame comprises fluoric cyclic carbonate, fluoro linear carbonate and alkyl-perfluoroalkyl ether; Described composite flame-retardant agent comprises phosphorus-nitrogen compound or halophosphoric acid ester complexes.
5. ternary lithium battery as claimed in claim 1, it is characterized in that, described fire retardant is tetrabromobisphenol A and triphenyl phosphate mixture.
6. the preparation method of a kind of ternary lithium battery as claimed in any one of claims 1 to 5, wherein, is characterized in that, comprise the following steps:
(1) LiNi is weighed respectively in mass ratio
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant, conductive black, PVDF and fire retardant are dissolved in 1-METHYLPYRROLIDONE solution, stir;
Wherein, 0<x<1,0<y<1,0<x+y<1;
(2) in solution, LiNi is added
xco
ymn
1-x-yo
2, pull an oar, obtained slurry;
(3) slurry is evenly coated on aluminium foil, carries out drying, rod pressure, cut obtained positive plate;
(4) positive plate obtained by utilization prepares ternary lithium battery;
Described LiNi
xco
ymn
1-x-yo
2, conductive black, PVDF and fire retardant mass ratio be: 85%-97%:1%-5%:1%-10%:2%-10%.
7. the preparation method of ternary lithium battery as claimed in claim 6, is characterized in that, described LiNi
xco
ymn
1-x-yo
2, conductive black and PVDF mass ratio be: 92%:1.5%:1.5%:5%.
8. the preparation method of ternary lithium battery as claimed in claim 6, it is characterized in that, described fire retardant comprises at least one in phosphorus flame retardant, halogenated flame retardant or composite flame-retardant agent.
9. the preparation method of ternary lithium battery as claimed in claim 8, it is characterized in that, described phosphorus flame retardant comprises alkyl phosphate, fluorinated phosphate ester and phosphonitrile compounds; Described halogenated flame comprises fluoric cyclic carbonate, fluoro linear carbonate and alkyl-perfluoroalkyl ether; Described composite flame-retardant agent comprises phosphorus-nitrogen compound or halophosphoric acid ester complexes.
10. the preparation method of ternary lithium battery as claimed in claim 6, it is characterized in that, described fire retardant is tetrabromobisphenol A and triphenyl phosphate mixture.
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105789683A (en) * | 2016-03-22 | 2016-07-20 | 山东大学 | Non-combustible lithium-sulfur or sodium-sulfur cell electrolyte solution and preparation method therefor |
CN107492660A (en) * | 2016-06-13 | 2017-12-19 | 宁德新能源科技有限公司 | Anode sizing agent, positive plate and lithium ion battery |
CN108695487A (en) * | 2017-04-07 | 2018-10-23 | 宁德时代新能源科技股份有限公司 | Positive plate and energy storage device |
CN108987793A (en) * | 2018-06-26 | 2018-12-11 | 桑顿新能源科技有限公司 | A kind of high security lithium ion battery and preparation method thereof |
CN109841908A (en) * | 2018-12-20 | 2019-06-04 | 上海力信能源科技有限责任公司 | A kind of high flame retardant preparation method of lithium ion battery |
CN111129467A (en) * | 2019-12-30 | 2020-05-08 | 国联汽车动力电池研究院有限责任公司 | Positive electrode slurry and preparation method thereof |
CN112331856A (en) * | 2020-11-03 | 2021-02-05 | 华东理工大学华昌聚合物有限公司 | Lithium ion battery electrode binder and preparation method and application thereof |
CN113036239A (en) * | 2021-02-26 | 2021-06-25 | 蜂巢能源科技有限公司 | Electrode plate and preparation method and application thereof |
CN113644275A (en) * | 2021-10-13 | 2021-11-12 | 深圳新宙邦科技股份有限公司 | Secondary battery |
US11502300B1 (en) | 2021-10-13 | 2022-11-15 | Shenzhen Capchem Technology Co., Ltd. | Secondary battery |
CN115832625A (en) * | 2021-12-02 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Flame retardant and secondary battery comprising same |
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JP2005149881A (en) * | 2003-11-14 | 2005-06-09 | Denso Corp | Nonaqueous electrolyte secondary battery |
JP2009016106A (en) * | 2007-07-03 | 2009-01-22 | Ntt Facilities Inc | Lithium ion secondary battery |
CN103782427A (en) * | 2011-09-02 | 2014-05-07 | 株式会社Ntt设施 | Nonaqueous electrolyte secondary cell |
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Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105789683A (en) * | 2016-03-22 | 2016-07-20 | 山东大学 | Non-combustible lithium-sulfur or sodium-sulfur cell electrolyte solution and preparation method therefor |
CN107492660A (en) * | 2016-06-13 | 2017-12-19 | 宁德新能源科技有限公司 | Anode sizing agent, positive plate and lithium ion battery |
CN107492660B (en) * | 2016-06-13 | 2020-04-24 | 宁德新能源科技有限公司 | Positive electrode slurry, positive plate and lithium ion battery |
CN108695487A (en) * | 2017-04-07 | 2018-10-23 | 宁德时代新能源科技股份有限公司 | Positive plate and energy storage device |
CN108987793B (en) * | 2018-06-26 | 2022-01-25 | 桑顿新能源科技(长沙)有限公司 | High-safety lithium ion battery and preparation method thereof |
CN108987793A (en) * | 2018-06-26 | 2018-12-11 | 桑顿新能源科技有限公司 | A kind of high security lithium ion battery and preparation method thereof |
CN109841908A (en) * | 2018-12-20 | 2019-06-04 | 上海力信能源科技有限责任公司 | A kind of high flame retardant preparation method of lithium ion battery |
CN111129467A (en) * | 2019-12-30 | 2020-05-08 | 国联汽车动力电池研究院有限责任公司 | Positive electrode slurry and preparation method thereof |
CN111129467B (en) * | 2019-12-30 | 2021-10-15 | 国联汽车动力电池研究院有限责任公司 | Positive electrode slurry and preparation method thereof |
CN112331856A (en) * | 2020-11-03 | 2021-02-05 | 华东理工大学华昌聚合物有限公司 | Lithium ion battery electrode binder and preparation method and application thereof |
CN113036239A (en) * | 2021-02-26 | 2021-06-25 | 蜂巢能源科技有限公司 | Electrode plate and preparation method and application thereof |
CN113036239B (en) * | 2021-02-26 | 2022-04-15 | 蜂巢能源科技有限公司 | Electrode plate and preparation method and application thereof |
CN113644275A (en) * | 2021-10-13 | 2021-11-12 | 深圳新宙邦科技股份有限公司 | Secondary battery |
US11502300B1 (en) | 2021-10-13 | 2022-11-15 | Shenzhen Capchem Technology Co., Ltd. | Secondary battery |
CN115832625A (en) * | 2021-12-02 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Flame retardant and secondary battery comprising same |
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Application publication date: 20160217 |
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