CN106129365B - High-safety lithium manganese iron phosphate battery - Google Patents
High-safety lithium manganese iron phosphate battery Download PDFInfo
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- CN106129365B CN106129365B CN201610694572.3A CN201610694572A CN106129365B CN 106129365 B CN106129365 B CN 106129365B CN 201610694572 A CN201610694572 A CN 201610694572A CN 106129365 B CN106129365 B CN 106129365B
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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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
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- 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 belongs to the technical field of lithium ion batteries and specifically relates to a high-safety lithium manganese iron phosphate battery. The high-safety lithium manganese iron phosphate battery comprises a positive plate, a negative plate, an isolating membrane, an electrolyte and a battery shell, wherein the positive plate includes a positive pole current collector and a positive pole active material layer which is coated on a surface of the positive pole current collector; the positive pole active material layer includes the following components by weight percentage: 90wt%-96wt% of positive pole active material, 1.5wt%-5wt% of positive pole conductive agent and 2wt%-5wt% of positive pole binding agent; the positive pole conductive agent is a mixture of conductive carbon black and at least one of a carbon nano tube or graphene; and the ratio of the conductive carbon black to at least another conductive agent is 1wt%:0.5wt% to 4wt%:1wt% based on the weight percentage in the positive pole active material layer; the isolating membrane is one of a polyolefin film or a non-woven cloth film; and the electrolyte is a high-temperature-resistant electrolyte. Compared with a nickel cobalt lithium manganate ternary battery and a lithium iron phosphate battery, the high-safety lithium manganese iron phosphate battery has relatively high weight specific energy and relatively high safety performance at the same time, has a long cycle life and is suitable for popularization and application in the field of new energy vehicles.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of iron manganese phosphate lithium battery of high security.
Background technology
Since 2015, the commercially available explosive growth of China's power train in vehicle application lithium ion battery.Meanwhile, application market pair
Performance of lithium ion battery requirement is increasingly stricter, especially the new state of power accumulator used for electric vehicle of in May, 2015 issue
Mark, the security to battery proposes requirement higher.
Security and energy density as power lithium-ion battery key index, be always the weight researched and solved in industry
Point.The current most power lithium-ion battery system of domestic and international application is mainly ferric phosphate lithium and ternary (nickel manganese cobalt or nickel cobalt
Three kinds of metallic elements of aluminium) system, but both systems are respectively provided with obvious advantage and shortcoming, it is impossible to fully meet lithium ion power electricity
The need for pond is developed.LiFePO4 system battery cycle life and security performance are excellent, but specific energy is difficult to more than 1401,4- fourths
Sultone/Kg.Ternary system battery specific energy can reach 1801,4- butane sultones/more than Kg, but keep high
While specific energy, cycle life can be significantly worse than LiFePO4 system battery, and security performance there are problems that it is larger.If
Can develop a kind of while having the battery of LiFePO4 high security, long-life and ternary high-energy-density characteristic concurrently, it will to power
Battery development brings tremendous influence.
The content of the invention
Not enough present in background technology in order to overcome, the present invention provides a kind of high security iron manganese phosphate lithium battery, pin
To current LiFePO4 and the deficiency of ternary system battery, there is provided a kind of both to ensure battery energy density, can improve again
The lithium ion battery of its security performance.
To reach above-mentioned purpose, the present invention is achieved through the following technical solutions：
A kind of high security iron manganese phosphate lithium battery, including positive plate, negative plate, barrier film, electrolyte and battery case,
Described positive plate includes plus plate current-collecting body and is coated on the positive electrode active material layer on plus plate current-collecting body surface, according to weight percent
Than meter, the positive electrode active material layer composition is as follows：
90~96wt% of positive active material
1.5~5wt% of positive conductive agent
2~5wt% of positive electrode binder
Wherein, positive active material includes component A and the components of component B two, and wherein component is that A is iron manganese phosphate for lithium, component B
It is nickle cobalt lithium manganate.
Further, described iron manganese phosphate for lithium is with the weight ratio of nickle cobalt lithium manganate：Iron manganese phosphate for lithium:Nickle cobalt lithium manganate=
10:90~50:50.
Further, the iron manganese phosphate for lithium uses material with carbon-coated surface and body phase iron ion doping, and molecular formula is LiMnxFe1- xPO4, wherein x scopes are 0.3~0.8；Described nickle cobalt lithium manganate molecular formula is LiNiyCozMn1-y-zO2, the wherein scope of y is
The scope of 0.3~0.8, z is 0.1~0.5.
Further, the positive conductive agent is that conductive black mixes with least one in CNT or Graphene, and
According to the percentage by weight meter in positive electrode active material layer, the conductive black is with the ratio of other at least one conductive agent
1wt%：0.5wt%~4wt%：1wt%.
Further, the plus plate current-collecting body is the aluminium foil that there is coating treatment on positive and negative surface, the coating be conductive black,
One kind in CNT or Graphene, the total coating thickness is 2 μm~5 μm.
Further, the negative plate includes negative current collector and is coated on the negative electrode active material on negative current collector surface
Layer, in percentage by weight, the negative electrode active material layer composition is as follows：
94~98wt% of negative electrode active material
0.5~2wt% of cathode conductive agent
1~5wt% of negative electrode binder
Wherein, negative electrode active material is at least one in Delanium, native graphite or carbonaceous mesophase spherules；
Cathode conductive agent is at least one in conductive black, CNT or Graphene；
Negative electrode binder includes sodium carboxymethylcellulose and two kinds of components of butadiene-styrene rubber.
Further, the barrier film is the one kind in polyolefin film or non-woven thin-film, and protective coating is contained on surface, institute
Protective coating is stated for Al2One kind in O3, SiO2, TiO2, MgO or CaO.
Further, the electrolyte be high temperature resistant electrolyte, main component be 11~14wt% of lithium salts, organic solvent 84~
88wt%, 0.5~2wt% of high temperature additive, the lithium salts are lithium hexafluoro phosphate, double lithium borates, difluoro bis phosphoric acid lithium and chlorine high
At least one mixing of sour lithium.
Further, the organic solvent mixing for ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate or propene carbonate
Bonding solvent.
Further, the high temperature additive is Isosorbide-5-Nitrae-butane sultones or 1,3- propane sultone and monoethanolamine
Mixing, and add linear polymeric phosphonitrile or cyclic phosphazene tripolymer.
Beneficial effects of the present invention：
To improve the problem of nickel-cobalt lithium manganate material security difference in the present invention, iron manganese phosphate for lithium is carried out physics therewith and is mixed
Close, iron manganese phosphate for lithium only has 1/3 of nickle cobalt lithium manganate or so due to particle diameter, can be distributed in after mixing nickle cobalt lithium manganate particle it
Between, nickel-cobalt lithium manganate material can be suppressed chain reaction occurs in the case of thermal runaway, be conducive to improving its thermally-stabilised
Property；To improve the problem of iron manganese phosphate for lithium poorly conductive, the on the one hand nickel-cobalt lithium manganate material more excellent with electric conductivity in the present invention
It is used in mixed way, nickle cobalt lithium manganate is played good conductive node by physical mixed and act on.Another aspect positive conductive agent is removed
Using conductive black known in those skilled in the art and CNT, graphene solution is also added, can be effectively improved just
Pole active material layer processing characteristics and electric conductivity.Plus plate current-collecting body selects the aluminium foil of coating treatment, conductive also for improving
Performance, meanwhile, can delay thermal runaway when the safety tests such as acupuncture, short circuit and extruding are carried out, improve security performance；In the present invention
The barrier film is the one kind in polyolefin film or non-woven thin-film, and protective coating is contained on surface.The protective coating is
Al2O3、SiO2、TiO2, one kind in MgO or CaO.Protective coating can be effectively improved membrane surface oxidation and thermal contraction, improve electricity
Pond service life, improves security performance；It is to improve electrolyte decomposition temperature using the main purpose of high temperature resistant electrolyte, while increasing
Strong its anti-flammability, makes battery high-temperature behavior and security performance get a promotion；The battery case by those skilled in the art public affairs
One kind in aluminum plastic film flexible package, aluminum hull, box hat or the plastic casing known.
Brief description of the drawings
Fig. 1 is the 1C discharge curves of embodiments of the invention 1,2 and comparative example 1,2；
Fig. 2 is the 1C charge and discharge cycles curves of embodiments of the invention 1,2 and comparative example 1,2；
Fig. 3 is that embodiments of the invention 1,2 overcharge curve with the 1C 6.3V of comparative example 1,2.
Specific embodiment
Below in conjunction with drawings and Examples of the invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments, is based on
Embodiment in the present invention, it is all other that this area control technical staff is obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1
The present embodiment is made using lamination flexible packaged battery pool process.
Positive active material content is iron manganese phosphate for lithium 20wt%, nickle cobalt lithium manganate 80wt% in the present embodiment.
The preparation method of anode pole piece is in the present embodiment：
1) material baking：According to 19wt%：75.3wt%：3wt%：2wt%：0.7wt% weighs iron manganese phosphate for lithium, nickel cobalt
LiMn2O4, Kynoar, conductive black and graphene solution.By iron manganese phosphate for lithium, nickle cobalt lithium manganate and conductive black powder
Baking 8 hours is vacuumized under the conditions of 120 DEG C, by Kynoar (molecular weight 1,000,000~1,100,000) powder under the conditions of 80 DEG C
Vacuumize baking 4 hours, using cassette cooker measurement moisture it is qualified after be cooled to less than 40 DEG C it is standby.
2) glue is prepared：1 part of Kynoar is added in 15 parts of N-methyl pyrrolidones, vacuum high-speed stirred 3 is small
When, preparation obtains the glue that viscosity is 1000~2500mPas.
3) anode sizing agent is prepared：Conductive black is added in glue, vacuum high-speed stirred 2 hours, adds Graphene molten
Liquid, vacuum high-speed stirred 1 hour.Then the uniform nickle cobalt lithium manganate of physical mixed and iron manganese phosphate lithium powder are added to slurry
In, vacuum high-speed stirred 3 hours.N-methyl pyrrolidones adjustment slurry viscosity is added, high-speed stirred 0.5 is small after adding every time
When, it is standby that sizing material is crossed 150 mesh sieves by measurement viscosity in 7000~9000mPas.
4) positive pole coil coating cloth：Anode sizing agent is coated by extrusion coating machine, foil uses Graphene coated aluminum foil,
Thickness is 20um, and it is 380g/m to be coated with two-sided surface density2, coating machine 8~12m/min of walking speed turns follow-up after coating qualified by baking.
5) prepared by anode pole piece：The positive pole volume after qualified by baking will be coated with carries out roll-in, roll-in compacted density 2.9~
3.0g/cc, it is desirable to which pole piece does not drop off good toughness.Positive pole volume after roll-in obtains positive plate by cross cutting, folded for further battery
Piece.
The preparation method of cathode pole piece is in the present embodiment：
By Delanium, conductive black, sodium carboxymethylcellulose and butadiene-styrene rubber with 95wt%：1wt%：1.5wt%：
2.5wt% ratios carry out slurry preparation, and solvent is deionized water, and final cathode size viscosity is 3000~5000mPas.So
After be coated, it is prepared by roll-in and cathode pole piece.
Battery production method is in the present embodiment：
Anode pole piece and cathode pole piece and protective coating barrier film are carried out into lamination, encapsulation, then vacuum bakeout is extremely at 90 DEG C
Moisture ＜ 500ppm.After qualified by baking inject high temperature resistant electrolyte, and by high temperature ageing, chemical conversion, high temperature ageing, take out very
Empty two envelopes obtain resultant battery.
After testing, 1C electric discharge specific energies are 1701,4- butane sultones/Kg to resultant battery in the present embodiment, and 1C fills
Residual capacity is the 96.3% of initial capacity after discharge cycles 500 times, can be by the safety test such as overcharging.
Embodiment 2
The present embodiment is made using lamination flexible packaged battery pool process.
Positive active material content is iron manganese phosphate for lithium 30wt%, nickle cobalt lithium manganate 70wt% in the present embodiment.
The preparation method of anode pole piece is in the present embodiment：
1) material baking：According to 28.2wt%：65.8wt%：3wt%：2wt%：1wt% weighs iron manganese phosphate for lithium, nickel cobalt
LiMn2O4, Kynoar, conductive black and graphene solution.By iron manganese phosphate for lithium, nickle cobalt lithium manganate and conductive black powder
Baking 8 hours is vacuumized under the conditions of 120 DEG C, by Kynoar (molecular weight 1,000,000~1,100,000) powder under the conditions of 80 DEG C
Vacuumize baking 4 hours, using cassette cooker measurement moisture it is qualified after be cooled to less than 40 DEG C it is standby.
2) glue is prepared：1 part of Kynoar is added in 15 parts of N-methyl pyrrolidones, vacuum high-speed stirred 3 is small
When, preparation obtains the glue that viscosity is 1000~2500mPas.
3) anode sizing agent is prepared：Conductive black is added in glue, vacuum high-speed stirred 2 hours, adds Graphene molten
Liquid, vacuum high-speed stirred 1 hour.Then the uniform nickle cobalt lithium manganate of physical mixed and iron manganese phosphate lithium powder are added to slurry
In, vacuum high-speed stirred 3 hours.N-methyl pyrrolidones adjustment slurry viscosity is added, high-speed stirred 0.5 is small after adding every time
When, it is standby that sizing material is crossed 150 mesh sieves by measurement viscosity in 7000~9000mPas.
4) positive pole coil coating cloth：Anode sizing agent is coated by extrusion coating machine, foil uses Graphene coated aluminum foil,
Thickness is 20um, and it is 380g/m to be coated with two-sided surface density2, coating machine 8~12m/min of walking speed turns follow-up after coating qualified by baking.
5) prepared by anode pole piece：The positive pole volume after qualified by baking will be coated with carries out roll-in, roll-in compacted density 2.7~
2.9g/cc, it is desirable to which pole piece does not drop off good toughness.Positive pole volume after roll-in obtains positive plate by cross cutting, folded for further battery
Piece.
The preparation method of cathode pole piece is in the present embodiment：
By Delanium, conductive black, sodium carboxymethylcellulose and butadiene-styrene rubber with 95wt%：1wt%：1.5wt%：
2.5wt% ratios carry out slurry preparation, and solvent is deionized water, and final cathode size viscosity is 3000~5000mPas.So
After be coated, it is prepared by roll-in and cathode pole piece.
Battery production method is in the present embodiment：
Anode pole piece and cathode pole piece and protective coating barrier film are carried out into lamination, encapsulation, then vacuum bakeout is extremely at 90 DEG C
Moisture ＜ 500ppm.After qualified by baking inject high temperature resistant electrolyte, and by high temperature ageing, chemical conversion, high temperature ageing, take out very
Empty two envelopes obtain resultant battery.
After testing, 1C electric discharge specific energies are 1601,4- butane sultones/Kg to resultant battery in the present embodiment, and 1C fills
Residual capacity is the 97.7% of initial capacity after discharge cycles 500 times, can be by the safety test such as overcharging.
Comparative example 1
The present embodiment is made using lamination flexible packaged battery pool process.
Positive active material content is only iron manganese phosphate for lithium in the present embodiment.
The preparation method of anode pole piece is in the present embodiment：
1) material baking：According to 92wt%：4wt%：3wt%：1wt% weighs iron manganese phosphate for lithium, Kynoar, conduction
Carbon black and graphene solution.Iron manganese phosphate for lithium and conductive black powder are vacuumized into baking 8 hours under the conditions of 120 DEG C, will be poly-
Vinylidene (molecular weight 1,000,000~1,100,000) powder vacuumizes baking 4 hours under the conditions of 80 DEG C, and water is measured using cassette cooker
Be cooled to after point content is qualified less than 40 DEG C it is standby.
2) glue is prepared：1 part of Kynoar is added in 15 parts of N-methyl pyrrolidones, vacuum high-speed stirred 3 is small
When, preparation obtains the glue that viscosity is 1000~2500mPas.
3) anode sizing agent is prepared：Conductive black is added in glue, vacuum high-speed stirred 2 hours, adds Graphene molten
Liquid, vacuum high-speed stirred 1 hour.Then iron manganese phosphate lithium powder is added in slurry, vacuum high-speed stirred 3 hours.Again plus
Enter N-methyl pyrrolidones adjustment slurry viscosity, high-speed stirred 0.5 hour after adding every time, measurement viscosity 7000~
Sizing material crossed into 150 mesh sieves during 9000mPas standby.
4) positive pole coil coating cloth：Anode sizing agent is coated by extrusion coating machine, foil uses Graphene coated aluminum foil,
Thickness is 20um, and it is 300g/m to be coated with two-sided surface density2, coating machine 10~14m/min of walking speed, after turning after coating qualified by baking
It is continuous.
5) prepared by anode pole piece：The positive pole volume after qualified by baking will be coated with carries out roll-in, roll-in compacted density 2.2~
2.25g/cc, it is desirable to which pole piece does not drop off good toughness.Positive pole volume after roll-in obtains positive plate by cross cutting, folded for further battery
Piece.
The preparation method of cathode pole piece is in the present embodiment：
By Delanium, conductive black, sodium carboxymethylcellulose and butadiene-styrene rubber with 95wt%：1wt%：1.5wt%：
2.5wt% ratios carry out slurry preparation, and solvent is deionized water, and final cathode size viscosity is 3000~5000mPas.So
After be coated, it is prepared by roll-in and cathode pole piece.
Battery production method is in the present embodiment：
Anode pole piece and cathode pole piece and protective coating barrier film are carried out into lamination, encapsulation, then vacuum bakeout is extremely at 90 DEG C
Moisture ＜ 500ppm.After qualified by baking inject high temperature resistant electrolyte, and by high temperature ageing, chemical conversion, high temperature ageing, take out very
Empty two envelopes obtain resultant battery.
After testing, 1C electric discharge specific energies are 1401,4- butane sultones/Kg to resultant battery in the present embodiment, and 1C fills
Residual capacity is the 98.3% of initial capacity after discharge cycles 500 times, can be by the safety test such as overcharging.
Comparative example 2
The present embodiment is made using lamination flexible packaged battery pool process.
Positive active material content is only nickle cobalt lithium manganate in the present embodiment.
The preparation method of anode pole piece is in the present embodiment：
1) material baking：According to 94.5wt%：3wt%：2wt%：0.5wt% weigh nickle cobalt lithium manganate, Kynoar,
Conductive black and graphene solution.Nickle cobalt lithium manganate and conductive black powder are vacuumized into baking 8 hours under the conditions of 120 DEG C,
Kynoar (molecular weight 1,000,000~1,100,000) powder is vacuumized into baking 4 hours under the conditions of 80 DEG C, is surveyed using cassette cooker
Amount moisture it is qualified after be cooled to less than 40 DEG C it is standby.
2) glue is prepared：1 part of Kynoar is added in 15 parts of N-methyl pyrrolidones, vacuum high-speed stirred 3 is small
When, preparation obtains the glue that viscosity is 1000~2500mPas.
3) anode sizing agent is prepared：Conductive black is added in glue, vacuum high-speed stirred 2 hours, adds Graphene molten
Liquid, vacuum high-speed stirred 1 hour.Then nickle cobalt lithium manganate powder is added in slurry, vacuum high-speed stirred 3 hours.Again plus
Enter N-methyl pyrrolidones adjustment slurry viscosity, high-speed stirred 0.5 hour after adding every time, measurement viscosity 7000~
Sizing material crossed into 150 mesh sieves during 9000mPas standby.
4) positive pole coil coating cloth：Anode sizing agent is coated by extrusion coating machine, foil uses Graphene coated aluminum foil,
Thickness is 20um, and it is 430g/m to be coated with two-sided surface density2, coating machine 8~10m/min of walking speed turns follow-up after coating qualified by baking.
5) prepared by anode pole piece：The positive pole volume after qualified by baking will be coated with carries out roll-in, roll-in compacted density 3.2~
3.4g/cc, it is desirable to which pole piece does not drop off good toughness.Positive pole volume after roll-in obtains positive plate by cross cutting, folded for further battery
Piece.
The preparation method of cathode pole piece is in the present embodiment：
By Delanium, conductive black, sodium carboxymethylcellulose and butadiene-styrene rubber with 95wt%：1wt%：1.5wt%：
2.5wt% ratios carry out slurry preparation, and solvent is deionized water, and final cathode size viscosity is 3000~5000mPas.So
After be coated, it is prepared by roll-in and cathode pole piece.
Battery production method is in the present embodiment：
Anode pole piece and cathode pole piece and protective coating barrier film are carried out into lamination, encapsulation, then vacuum bakeout is extremely at 90 DEG C
Moisture ＜ 500ppm.After qualified by baking inject high temperature resistant electrolyte, and by high temperature ageing, chemical conversion, high temperature ageing, take out very
Empty two envelopes obtain resultant battery.
After testing, 1C electric discharge specific energies are 1801,4- butane sultones/Kg to resultant battery in the present embodiment, and 1C fills
Residual capacity is the 93.5% of initial capacity after discharge cycles 500 times, it is impossible to by the safety test such as overcharging.
Experimental analysis：
1st, 1C electric discharges specific energy
Resultant battery prepared by embodiment 1,2 and comparative example 1,2 is at normal temperatures using 1C constant-current charges to 4.2V
And constant pressure is to 0.02C, after shelving 10 minutes, with 1C constant-current discharges to 2.8V, discharge electricity amount is recorded, and according to discharge electricity amount and electricity
Pond weight calculates 1C electric discharge specific energies.Comparing result is shown in Table 1 and Fig. 1.
The different embodiment 1C electric discharges specific energy comparing results of table 1
2nd, 1C charge and discharge cycles 500 times
Resultant battery prepared by embodiment 1,2 and comparative example 1,2 is at normal temperatures using 1C constant-current charges to 4.2V
And constant pressure is to 0.02C, after shelving 10 minutes, with 1C constant-current discharges to 2.8V, compare after so repeating charge-discharge test 500 times
Compared with the 500th discharge capacity and initial discharge capacity.Comparing result is shown in Table 2 and Fig. 2.
Difference embodiment 1C 500 comparing results of charge and discharge cycles of table 2
| Experiment condition | 1C charge and discharge cycles 500 times |
| Embodiment 1 | 96.3% |
| Embodiment 2 | 97.7% |
| Comparative example 1 | 98.3% |
| Comparative example 2 | 93.5% |
3rd, 1C 6.3V are overcharged
Resultant battery prepared by embodiment 1,2 and comparative example 1,2 is at normal temperatures using 1C constant-current charges to 4.2V
And constant pressure is to 0.02C, after shelving 10 minutes, 6.3V (1.5 times of set upper limit voltage) is charged to 1C or the charging interval reaches 1
Stop charging after hour, and observe 1 hour.Comparing result is shown in Table 3 and Fig. 3.
The difference embodiment 1C of table 3 6.3V overcharge comparing result
| Experiment condition | 1C 6.3V are overcharged |
| Embodiment 1 | Pass through |
| Embodiment 2 | Pass through |
| Comparative example 1 | Pass through |
| Comparative example 2 | Catching fire |
Be can be seen that from table 1-3, iron manganese phosphate for lithium battery performance prepared by the present invention is relatively better than existing iron manganese phosphate for lithium electricity
Pond.
To improve the problem of nickel-cobalt lithium manganate material security difference in the present invention, iron manganese phosphate for lithium is carried out physics therewith and is mixed
Close, iron manganese phosphate for lithium only has 1/3 of nickle cobalt lithium manganate or so due to particle diameter, can be distributed in after mixing nickle cobalt lithium manganate particle it
Between, nickel-cobalt lithium manganate material can be suppressed chain reaction occurs in the case of thermal runaway, be conducive to improving its thermally-stabilised
Property；To improve the problem of iron manganese phosphate for lithium poorly conductive, the on the one hand nickel-cobalt lithium manganate material more excellent with electric conductivity in the present invention
It is used in mixed way, nickle cobalt lithium manganate is played good conductive node by physical mixed and act on.Another aspect positive conductive agent is removed
Using conductive black known in those skilled in the art and CNT, graphene solution is also added, can be effectively improved just
Pole active material layer processing characteristics and electric conductivity.Plus plate current-collecting body selects the aluminium foil of coating treatment, conductive also for improving
Performance, meanwhile, can delay thermal runaway when the safety tests such as acupuncture, short circuit and extruding are carried out, improve security performance；In the present invention
The barrier film is the one kind in polyolefin film or non-woven thin-film, and protective coating is contained on surface.The protective coating is
Al2O3、SiO2、TiO2, one kind in MgO or CaO.Protective coating can be effectively improved membrane surface oxidation and thermal contraction, improve electricity
Pond service life, improves security performance；It is to improve electrolyte decomposition temperature using the main purpose of high temperature resistant electrolyte, while increasing
Strong its anti-flammability, makes battery high-temperature behavior and security performance get a promotion；The battery case by those skilled in the art public affairs
One kind in aluminum plastic film flexible package, aluminum hull, box hat or the plastic casing known.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical
Cross above preferred embodiment to be described in detail the present invention, it is to be understood by those skilled in the art that can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (4)
1. a kind of high security iron manganese phosphate lithium battery, including positive plate, negative plate, barrier film, electrolyte and battery case, its
It is characterised by：The electrolyte be high temperature resistant electrolyte, main component be 11~14wt% of lithium salts, 84~88wt% of organic solvent,
0.5~2wt% of high temperature additive, the lithium salts is in lithium hexafluoro phosphate, double lithium borates, difluoro bis phosphoric acid lithium and lithium perchlorate
At least one, the organic solvent is for ethylene carbonate, dimethyl carbonate and selected from methyl ethyl carbonate or propene carbonate
A kind of mixed solvent, the high temperature additive is selected from Isosorbide-5-Nitrae-butane sultones or 1,3- propane sultone
One kind mixes with monoethanolamine, and adds linear polymeric phosphonitrile or cyclic phosphazene tripolymer, and positive plate includes plus plate current-collecting body and painting
, in the positive electrode active material layer on plus plate current-collecting body surface, in percentage by weight, the positive electrode active material layer composition is such as cloth
Under：
90~96wt% of positive active material
1.5~5wt% of positive conductive agent
2~5wt% of positive electrode binder
Wherein, positive active material includes component A and the components of component B two, and wherein component A is iron manganese phosphate for lithium, and component B is nickel cobalt
LiMn2O4,
The preparation method of positive plate is：
1）Material is toasted：Iron manganese phosphate for lithium, nickle cobalt lithium manganate, Kynoar, conductive black and graphite are weighed according to formula ratio
Alkene solution, baking 8 hours is vacuumized by iron manganese phosphate for lithium, nickle cobalt lithium manganate and conductive black powder under the conditions of 120 DEG C, will be divided
Son amount vacuumizes baking 4 hours for 1,000,000~1,100,000 Kynoar powder under the conditions of 80 DEG C, is measured using cassette cooker
Be cooled to after moisture is qualified less than 40 DEG C it is standby；
2）Glue is prepared：1 part of Kynoar is added in 15 parts of N-methyl pyrrolidones, vacuum high-speed stirred 3 hours is matched somebody with somebody
The glue that viscosity is 1000~2500mPas is obtained；
3）Anode sizing agent is prepared：Conductive black is added in glue, vacuum high-speed stirred 2 hours, adds graphene solution, very
, then be added in slurry for the uniform nickle cobalt lithium manganate of physical mixed and iron manganese phosphate lithium powder, very by empty high-speed stirred 1 hour
Empty high-speed stirred 3 hours, adds N-methyl pyrrolidones adjustment slurry viscosity, and high-speed stirred 0.5 hour after adding every time is surveyed
It is standby that sizing material is crossed 150 mesh sieves by amount viscosity in 7000~9000mPas；
4）Positive pole coil coating cloth：Anode sizing agent is coated by extrusion coating machine, foil uses Graphene coated aluminum foil, thickness
It it is 20 μm, it is 380g/m to be coated with two-sided surface density2, coating machine 8~12m/min of walking speed turns follow-up after coating qualified by baking；
5）It is prepared by positive plate：Will be coated with qualified by baking after positive pole volume carry out roll-in, roll-in compacted density in 2.9~3.0g/cc,
It is required that pole piece does not drop off good toughness, the positive pole volume after roll-in obtains positive plate by cross cutting, for further battery lamination；
The preparation method of negative plate is：
By Delanium, conductive black, sodium carboxymethylcellulose and butadiene-styrene rubber with 95wt%：1wt%：1.5wt%：2.5wt% ratios
Example carries out slurry preparation, and solvent is deionized water, and final cathode size viscosity is 3000~5000mPas, is then applied
It is prepared by cloth, roll-in and negative plate；
Battery production method is：
Positive plate and negative plate and barrier film are carried out into lamination, encapsulation, then at 90 DEG C vacuum bakeout to moisture ＜
500ppm, injects high temperature resistant electrolyte after qualified by baking, and by high temperature ageing, chemical conversion, high temperature ageing, vacuumize two envelopes and obtain
Resultant battery.
2. a kind of high security iron manganese phosphate lithium battery according to claim 1, it is characterised in that：Described iron manganese phosphate
Lithium is with the weight ratio of nickle cobalt lithium manganate：Iron manganese phosphate for lithium:Nickle cobalt lithium manganate=10:90~50:50.
3. a kind of high security iron manganese phosphate lithium battery according to claim 1 and 2, it is characterised in that：The manganese phosphate
Iron lithium uses material with carbon-coated surface and body phase iron ion doping, and molecular formula is LiMnxFe1-xPO4, wherein x scopes are 0.3~0.8；Institute
The nickle cobalt lithium manganate molecular formula stated is LiNiyCozMn1-y-zO2, the wherein scope of y is that the scope of 0.3~0.8, z is 0.1~0.5.
4. high security iron manganese phosphate lithium battery according to claim 1, it is characterised in that：The barrier film is polyolefin
Protective coating is contained on one kind in film or non-woven thin-film, surface, and the protective coating is Al2O3、SiO2、TiO2, MgO or
One kind in CaO.
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