CN109860604A - A kind of lithium iron phosphate dynamic battery and its manufacturing method - Google Patents
A kind of lithium iron phosphate dynamic battery and its manufacturing method Download PDFInfo
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- CN109860604A CN109860604A CN201910082261.5A CN201910082261A CN109860604A CN 109860604 A CN109860604 A CN 109860604A CN 201910082261 A CN201910082261 A CN 201910082261A CN 109860604 A CN109860604 A CN 109860604A
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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
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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
- 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
Abstract
The invention discloses a kind of lithium iron phosphate dynamic batteries and preparation method thereof, the battery includes positive plate, negative electrode tab, wet process diaphragm, low-temperature electrolyte and plastic shell, wherein: positive plate includes utter misery metal foil and the positive electrode coated in utter misery metal foil surface, and positive electrode includes LiFePO4, CNT, conductive carbon black and acrylonitrile polymer binder；Negative electrode tab includes negative current collector and the negative electrode material coated in negative current collector surface, and negative electrode material includes graphite, cathode conductive agent, CMC and acrylonitrile polymer binder；Low-temperature electrolyte includes carbonate solvent, film for additive and lithium hexafluoro phosphate；Wet process diaphragm includes polyethylene layer and the ceramic layer for being compounded in polyethylene layer surface.Charging capacity of the lithium iron phosphate dynamic battery prepared by the present invention under -20 DEG C of 1C environment reaches 90% or more, and -50 DEG C of 1C environment discharge capacities reach 95% or more, has excellent low temperature charge-discharge performance.
Description
Technical field
The present invention relates to field of lithium ion battery, and in particular to a kind of lithium iron phosphate dynamic battery and its manufacturing method.
Background technique
Petroleum resources are increasingly depleted, and before the arriving of next oil crisis, greatly developing pure electric automobile is only choosing.
LiFePO4 lithium dynamical battery is the green high-capacity environment-protecting battery occurred the 1990s, has energy density height, environment friend
It gets well, memory-less effect, have extended cycle life, prominent advantage, the electric car, military ideal light high-energy power such as self discharge is few
Source.Therefore, lithium ion battery becomes the hot spot that battery circle is studied extensively in recent years.But lithium iron phosphate dynamic battery is in low temperature ring
Charge under border, discharge it is all highly difficult, cause battery enter winter or extremely cold place can not normal use, country's energy at present
The technical performance reached is that 0 DEG C of charging capacity reaches nominal capacity 60%, and -20 DEG C of discharge capacities reach the 80% of nominal capacity, put
Electrical power can only achieve 60%.Cause lithium iron phosphate dynamic battery that can not work normally in 0 DEG C of environment below, the present invention is in mesh
Preceding lithium iron phosphate dynamic battery be technically increased to -20 DEG C of 1C charging to reach 90%, -50 DEG C of 1C can be reached with discharge capacity
To 95%, discharge power reaches 90%.
Summary of the invention
The object of the present invention is to provide a kind of lithium iron phosphate dynamic battery and its manufacturing methods, to solve phosphorus in the prior art
Sour iron lithium dynamical battery charges at low ambient temperatures, difficult problem of discharging.
Technical solution: to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of lithium iron phosphate dynamic battery, including positive plate, negative electrode tab, wet process diaphragm, low-temperature electrolyte and plastic shell,
In:
The positive plate includes utter misery metal foil and the positive electrode coated in utter misery metal foil surface, the utter misery metal foil
Outer layer is graphene layer, and the positive electrode includes LiFePO4, CNT, conductive carbon black and acrylonitrile polymer binder；
The negative electrode tab includes negative current collector and the negative electrode material coated in negative current collector surface, and negative electrode material includes stone
Ink, cathode conductive agent, CMC and acrylonitrile polymer binder；
The low-temperature electrolyte includes carbonate solvent, film for additive and lithium hexafluoro phosphate, and the carbonate solvent includes carbon
Vinyl acetate, methyl ethyl carbonate, ethyl acetate, propene carbonate；The film for additive includes vinylene carbonate, sulfurous acid
Acrylic ester；
The wet process diaphragm includes polyethylene layer and the ceramic layer for being compounded in polyethylene layer surface.
Further scheme, ethylene carbonate in the low-temperature electrolyte, methyl ethyl carbonate, ethyl acetate, propene carbonate,
Vinylene carbonate, propylene sulfite weight ratio be (15-20): (45-50): (25-30): 10: 2:2, six
The substance withdrawl syndrome of lithium fluophosphate is 1mol/L-1.5 mol/L.
Further scheme, the weight of LiFePO4, CNT, conductive carbon black, acrylonitrile polymer binder in the positive electrode
Amount is than being (90-94): (1-2): (3-5): (1-3)；The LiFePO4 uses the median particle diameter (D50) of primary particle for 100
Nm -300nm, the median particle diameter (D50) of secondary granulation are 1 μm -3 μm.
Further scheme, the coating surface density of the positive electrode are 290g/cm2-310g/cm2, compacted density 2g/
cm3-2.5g/cm3。
Further scheme, the cathode conductive agent include CNT and conductive carbon black, and the graphite is unformed carbon-coated people
Graphite is made, median particle diameter (D50) is 8 μm -10 μm.
Further scheme, the weight of graphite, CNT, conductive carbon black, CMC, acrylonitrile polymer binder in the negative electrode material
Amount is than being (92-95): (1-3): (2-4): (0.2-1): (2-4).
Further scheme, the coating surface density of the negative electrode material are 140g/cm2-160g/cm2, compacted density 1g/
cm3-2g/cm3。
Further scheme, the polyethylene layer with a thickness of 16 μm, glass transition temperature is -70 DEG C, porosity 40-45%,
Air permeability is 170-190；The ceramic layer with a thickness of 4 μm.
Further scheme, the material of the plastic shell are PP, and the metal foil is aluminium foil or copper foil, the negative pole currect collecting
Body is copper foil.
It is a further object to provide the preparation methods of above-mentioned lithium iron phosphate dynamic battery, include the following steps:
(A) deionized water, uniform stirring is added after mixing LiFePO4, CNT, conductive carbon black and acrylonitrile polymer binder
At the anode sizing agent with mobility and caking property, anode sizing agent is coated in utter misery metal foil, dry, compacting is made just
Pole piece；
(B) will graphite, cathode conductive agent, CMC and acrylonitrile polymer binder mix after be added deionized water, uniform stirring at
Negative electrode slurry is coated on negative current collector by the negative electrode slurry with mobility and caking property, dry, and cathode is made in compacting
Piece；
(C) methyl ethyl carbonate, methyl ethyl carbonate, ethyl acetate, propene carbonate, vinylene carbonate, sulfurous acid propylene are weighed
After ester wiring solution-forming, lithium hexafluoro phosphate is added, obtains low-temperature electrolyte；
(D) positive plate, negative electrode tab are separated with wet process diaphragm and build up battery core, battery core is put into baking oven baking, tests battery core moisture,
Plastic shell is packed into when moisture is in 300ppm or less, then by battery core, injects low-temperature electrolyte, electrolyte content 5.5g/Ah, 40
DEG C -50 DEG C are melted into after infiltration three days, shelved after chemical conversion 15 days again partial volume to get lithium iron phosphate dynamic battery.
The utility model has the advantages that
(1) positive plate of the invention selects utter misery metal foil as plus plate current-collecting body, and the graphene layer on surface layer makes itself and anode
The contact resistance of material is low, bond strength is high, and the cycle performance of battery can be improved；With CNT and conductive carbon in positive electrode
Black cooperate is used as positive conductive agent, and conductive black and positive electrode are combined closely by nanotube, form extensive net
Network structure, effectively improves the conductive capability of positive conductive agent, so that battery be made also to be able to maintain higher lithium ion at low temperature
Diffusion velocity；It selects acrylonitrile polymer as binder, substantially increases linear ion conducting, improve the ion-conductance of anode
Conductance, in addition, acrylonitrile polymer has preferable dispersion in water compared with PVDF binder conventional in the prior art
Property, in preparation process, there can be environment friendly while reducing cost using water consumption substitution NMP as solvent.
(2) present invention passes through the composition and dosage of optimization low-temperature electrolyte, and the selection of ethyl acetate and propene carbonate is big
The conductivity of electrolyte is improved greatly, and ethyl acetate molecular weight is lower, and fusing point is -84 DEG C, and viscosity is 0.4/ (mPas), carbonic acid
The dielectric constant of acrylic ester is 66c/v.m, and fusing point is -49 DEG C, and ethylene carbonate has high dielectric constant and efficient film forming effect
As film for additive, the internal resistance that forms a film is small for fruit, vinylene carbonate and propylene sulfite, so that carbonate solvent has Gao Jie
Electric constant can guarantee the solubility of lithium salts, and the formula of electrolyte is simple, is easily configured, and low-temperature conductivity is high, in low temperature
Under be more advantageous to the migration of lithium ion, be conducive to the low temperature charge-discharge performance for improving battery.
(3) battery case is PP plastic shell, can play heat-insulated and heat build-up effect, prevent temperature conduction and charge and discharge
The loss of temperature in the process.
(4) wet process diaphragm of the invention has ceramic layer, and ceramic layer can improve the wellability of polyethylene layer barrier film base material
And thermal stability, and can be used as the high safety diaphragm of lithium ion battery, improve lithium ion conduction rate.
(5) charging capacity of the lithium iron phosphate dynamic battery prepared by the present invention under -20 DEG C of 1C environment reaches 90% or more, -
50 DEG C of 1C environment discharge capacities reach 95% or more, have excellent low temperature charge-discharge performance.
Detailed description of the invention
Fig. 1 is the low temperature charging curve of conventional batteries prepared by comparative example 1；
Fig. 2 is the low temperature discharge curve of conventional batteries prepared by comparative example 1；
Fig. 3 is the low temperature charging curve of battery prepared by embodiment 1；
Fig. 4 is the low temperature discharge curve of battery prepared by embodiment 1.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be further explained.Obviously, described embodiment is this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
It should be noted that associated materials are obtained from the purchase of following company in this test:
Utter misery aluminium foil, Guangzhou nano new material Science and Technology Ltd.；Unformed carbon-coated artificial graphite, Tianjin Bei Teruixin energy
Source Science and Technology Ltd.；Wet process diaphragm, Shanghai Enjie New Material Technology Co., Ltd.；Common motive power electrolyte, Beijing
Chemistry institute.
Comparative example 1 prepares conventional batteries
(A) LiFePO4 in positive electrode, conductive carbon black, KS-6, PVDF weight ratio be 93:3:1:3, after weighing mixing, with
NMP is solvent, and anode sizing agent is coated on aluminium foil by uniform stirring at the anode sizing agent with mobility and caking property, coating
Surface density is 300g/cm2, compacted density 2.2g/cm3, positive plate is made；
(B) graphite in negative electrode material, CMC, SBR, conductive carbon black weight ratio be 91.5:1:2:5.5, wherein graphite is ordinary people
Make graphite, median particle diameter (D50) is 10 μm, is added deionized water after mixing, and uniform stirring is at mobility and caking property
Negative electrode slurry is coated on copper foil by negative electrode slurry, and coating surface density is 150g/cm2, compacted density 1.56g/cm3, it is made
Negative electrode tab；
(C) common motive power electrolyte is selected；
(D) positive plate, negative electrode tab are separated with 25 μm of PP dry method diaphragms and builds up battery core, battery core is put into baking oven baking, test electricity
Core moisture, moisture requirement are 300ppm hereinafter, battery core is packed into plastic shell again, inject common motive power electrolyte, electrolyte
Amount be 1100g, infiltration three days after be melted into, shelved after chemical conversion 15 days again partial volume to get conventional 200Ah aluminum-shell battery.
Conventional batteries prepared by test comparison example 1 are in -20 DEG C of 1C, 0 DEG C of 1C low temperature charging and -20 DEG C of 1C, -50 DEG C of 1C low temperature
Discharge performance；Test curve difference is as depicted in figs. 1 and 2；It is filled from figure 1 it appears that conventional batteries can not carry out -20 DEG C of 1C
Electricity, voltage are directly raised to ceiling restriction voltage, and polarization phenomena are serious, can only meet 0 DEG C of 1C charging, and charging capacity can only achieve
70%.From figure 2 it can be seen that -50 DEG C of 1C discharge capacities of conventional batteries are 30%, it is 2.01V that inflection point, which occurs, in voltage, then rise
Situation, -20 DEG C of 1C discharge capacities can reach 85%, can only meet -20 DEG C of discharge performances.
Embodiment 1
(A) LiFePO4 in positive electrode, conductive carbon black, CNT, acrylonitrile polymer binder weight ratio be 93:3:1:3,
Deionized water is added after mixing, anode sizing agent is coated in and applies at the anode sizing agent with mobility and caking property by uniform stirring
In charcoal metal foil, coating surface density is 300g/cm2, compacted density 2.2g/cm3, dry, positive plate is made in compacting；
(B) graphite in negative electrode material, CMC, acrylonitrile polymer binder, conductive carbon black, CNT weight ratio be 91.5:0.2:
2.8:3.5:2, wherein graphite is unformed carbon-coated artificial graphite, and median particle diameter is 10 μm, and deionized water is added after mixing,
Negative electrode slurry is coated on copper foil by uniform stirring at the negative electrode slurry with mobility and caking property, and coating surface density is
152g/cm2, compacted density 1.52g/cm3Dry, negative electrode tab is made in compacting；
(C) methyl ethyl carbonate, methyl ethyl carbonate, ethyl acetate, propene carbonate, vinylene carbonate, propylene sulfite
Weight ratio is 15:50:25:10:2:2, after wiring solution-forming, lithium hexafluoro phosphate is added, the substance withdrawl syndrome of lithium hexafluoro phosphate is
1.3mol/L obtains low-temperature electrolyte；
(D) positive plate, negative electrode tab are separated with wet process diaphragm and build up battery core, battery core is put into baking oven baking, tests battery core moisture,
Moisture requirement is 300ppm hereinafter, battery core is packed into plastic shell again, injects low-temperature electrolyte, electrolyte content 1100g, infiltration
Be melted into after three days, shelved after chemical conversion 15 days again partial volume to get lithium iron phosphate dynamic battery.
The battery that test is prepared according to the present embodiment is in -20 DEG C of 1C low temperature chargings and -50 DEG C of 1C low temperature performances；
Test curve difference is as shown in Figure 3 and Figure 4；From figure 3, it can be seen that -20 DEG C of 1C charging capacitys reach 195Ah, and voltage is line
Property rise, reach the 97.5% of nominal capacity.From fig. 4, it can be seen that -50 DEG C of 1C discharge capacities reach 200Ah, voltage knee is
2.79V reaches 2.5V protection voltage or more, reaches the 100% of nominal capacity.It can be seen that compared with comparative example test result, this reality
It is excellent to apply the charge-discharge performance of battery that example is prepared at low temperature.So to be able to solve battery low in -20 DEG C of 1C by the present invention
The problem of temperature charging and -50 DEG C of 1C low temperature discharge hardly possiblies.
Embodiment 2
(A) LiFePO4 in positive electrode, conductive carbon black, CNT, acrylonitrile polymer binder weight ratio be 91.5:4:2:
2.5, deionized water is added after mixing, uniform stirring coats anode sizing agent at the anode sizing agent with mobility and caking property
In utter misery metal foil, coating surface density is 310g/cm2, compacted density 2.2g/cm3, dry, positive plate is made in compacting；
(B) graphite in negative electrode material, CMC, acrylonitrile polymer binder, conductive carbon black, CNT weight ratio be 92.5:0.5:
2:2:3, wherein graphite is unformed carbon-coated artificial graphite, and median particle diameter is 8 μm, deionized water is added after mixing, uniformly
The negative electrode slurry with mobility and caking property is stirred into, negative electrode slurry is coated on copper foil, coating surface density is 152g/
cm2, compacted density 1.52g/cm3Dry, negative electrode tab is made in compacting；
(C) methyl ethyl carbonate, methyl ethyl carbonate, ethyl acetate, propene carbonate, vinylene carbonate, propylene sulfite
Weight ratio is 20:45:30:10: 2:2, and after wiring solution-forming, lithium hexafluoro phosphate, the amount of the substance of lithium hexafluoro phosphate is added
Concentration is 1.3mol/L, obtains low-temperature electrolyte;
(D) positive plate, negative electrode tab are separated with wet process diaphragm and build up battery core, battery core is put into baking oven baking, tests battery core moisture,
Moisture requirement is 300ppm hereinafter, battery core is packed into plastic shell again, injects low-temperature electrolyte, electrolyte content 1100g, infiltration
Be melted into after three days, shelved after chemical conversion 15 days again partial volume to get lithium iron phosphate dynamic battery.
Claims (10)
1. a kind of lithium iron phosphate dynamic battery, it is characterised in that: including positive plate, negative electrode tab, wet process diaphragm, low-temperature electrolyte and
Plastic shell, in which:
The positive plate includes utter misery metal foil and the positive electrode coated in utter misery metal foil surface, the utter misery metal foil
Outer layer is graphene layer, and the positive electrode includes LiFePO4, CNT, conductive carbon black and acrylonitrile polymer binder；
The negative electrode tab includes negative current collector and the negative electrode material coated in negative current collector surface, and negative electrode material includes stone
Ink, cathode conductive agent, CMC and acrylonitrile polymer binder；
The low-temperature electrolyte includes carbonate solvent, film for additive and lithium hexafluoro phosphate, and the carbonate solvent includes carbon
Vinyl acetate, methyl ethyl carbonate, ethyl acetate, propene carbonate；The film for additive includes vinylene carbonate, sulfurous acid
Acrylic ester；
The wet process diaphragm includes polyethylene layer and the ceramic layer for being compounded in polyethylene layer surface.
2. lithium iron phosphate dynamic battery according to claim 1, it is characterised in that: ethylene carbonate in the low-temperature electrolyte
Ester, methyl ethyl carbonate, ethyl acetate, propene carbonate, vinylene carbonate, propylene sulfite weight ratio be (15-20):
(45-50): (25-30): 10: 2:2, the substance withdrawl syndrome of the lithium hexafluoro phosphate is 1mol/L-1.5 mol/L.
3. lithium iron phosphate dynamic battery according to claim 1, it is characterised in that: LiFePO4 in the positive electrode,
CNT, conductive carbon black, acrylonitrile polymer binder weight ratio be (90-94): (1-2): (3-5): (1-3).
4. lithium iron phosphate dynamic battery according to claim 1, it is characterised in that: the coating surface density of the positive electrode
For 300g/cm2-310g/cm2, compacted density 2g/cm3-2.5g/cm3。
5. lithium iron phosphate dynamic battery according to claim 1, it is characterised in that: the cathode conductive agent include CNT and
Conductive carbon black；The graphite is unformed carbon-coated artificial graphite.
6. lithium iron phosphate dynamic battery according to claim 5, it is characterised in that: graphite in the negative electrode material, CNT,
Conductive carbon black, CMC, acrylonitrile polymer binder weight ratio be (92-95): (1-3): (2-4): (0.2-1): (2-4).
7. lithium iron phosphate dynamic battery according to claim 1, it is characterised in that: the coating surface density of the negative electrode material
For 140g/cm2-160g/cm2, compacted density 1g/cm3-2g/cm3。
8. lithium iron phosphate dynamic battery according to claim 1, it is characterised in that: the glass transition temperature of the polyethylene layer
It is -70 DEG C, porosity 40-45%, air permeability 170-190.
9. lithium iron phosphate dynamic battery according to claim 1, it is characterised in that: the material of the plastic shell is PP,
The metal foil is aluminium foil or copper foil, and the negative current collector is copper foil.
10. the preparation method of the lithium iron phosphate dynamic battery as described in claim 1-9 is any, it is characterised in that: including as follows
Step:
(A) after weighing LiFePO4, CNT, conductive carbon black and the mixing of acrylonitrile polymer binder, deionized water is added, uniformly
The anode sizing agent with mobility and caking property is stirred into, anode sizing agent is coated in utter misery metal foil, it is dry, it is compacted, system
At positive plate；
(B) after weighing graphite, cathode conductive agent, CMC and the mixing of acrylonitrile polymer binder, deionized water is added, uniformly stirs
The negative electrode slurry with mobility and caking property is mixed, negative electrode slurry is coated on negative current collector, dry, compacting is made
Negative electrode tab；
(C) methyl ethyl carbonate, methyl ethyl carbonate, ethyl acetate, propene carbonate, vinylene carbonate, sulfurous acid propylene are weighed
After ester wiring solution-forming, lithium hexafluoro phosphate is added, obtains low-temperature electrolyte；
(D) positive plate, negative electrode tab are separated with wet process diaphragm and build up battery core, battery core is put into baking oven baking, tests battery core moisture,
Plastic shell is packed into when moisture is in 300ppm or less, then by battery core, injects low-temperature electrolyte, electrolyte content 5.5g/Ah, 40
DEG C -50 DEG C are melted into after infiltration three days, shelved after chemical conversion 15 days again partial volume to get lithium iron phosphate dynamic battery.
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| CN114122406A (en) * | 2022-01-25 | 2022-03-01 | 成都特隆美储能技术有限公司 | Preparation method of graphene modified lithium iron phosphate and lithium iron phosphate |
| CN114400300A (en) * | 2022-03-02 | 2022-04-26 | 上海兰钧新能源科技有限公司 | Lithium iron phosphate positive plate, preparation method and battery |
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Application publication date: 20190607 |