CN110391414A - A kind of high energy density polymer lithium ion battery and preparation method thereof - Google Patents
A kind of high energy density polymer lithium ion battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of high energy density polymer lithium ion battery and preparation method thereof, which mainly includes positive plate, negative electrode tab, porous isolating membrane and organic electrolyte.The positive plate mainly contains cobalt acid lithium, the negative electrode tab mainly contains silicon series composite material, the isolation film is aluminum oxide and the mixed painting isolation film of Kynoar (PVDF), and the organic electrolyte is made of lithium salts, carbonic ester, carboxylate and various additives.Polymer Li-ion battery operating voltage range of the invention is 4.4V~3.0V, has high-energy density, battery cycle life is good, 1C charge and discharge normal temperature circulation 500 weeks, 80% or more capacity retention ratio；High temperature and low temperature performance excellent, 55 degree of high temperature discharges, 98% or more capacity retention ratio, the minus 20 degree of electric discharges of low temperature, 60% or more capacity retention ratio.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of high energy density polymer lithium ion battery and
Preparation method.
Background technique
Lithium ion battery is widely used in automobile, storage due to the advantages that its is environmental-friendly, energy density is high, good cycle
The fields such as energy, electronic product.Polymer Li-ion battery energy density is higher with respect to liquid lithium ionic cell, and battery appearance
It can customize as needed, it is especially welcome in electronics field.With electronic product make rapid progress variation, to polymer lithium from
The energy density requirement of sub- battery is also higher and higher, and the energy density of battery is common, causes battery capacity low, causes electronic product
Stand-by time and shorter using the time, largely effect on the usage experience of consumer, be badly in need of proposing a kind of electricity of high-energy density
Pond solves problems.
Summary of the invention
The purpose of the present invention is to solve drawbacks described above in the prior art, provide a kind of high energy density polymer lithium
Ion battery and preparation method thereof, the polymer Li-ion battery operating voltage range are 4.4V~3.0V, battery cycle life
It is good, 1C charge and discharge normal temperature circulation 500 weeks, 80% or more capacity retention ratio；High temperature and low temperature performance excellent, 55 degree of high temperature discharges hold
Measure 98% or more conservation rate, the minus 20 degree of electric discharges of low temperature, 60% or more capacity retention ratio.
The first purpose of this invention can be reached by adopting the following technical scheme that:
A kind of high energy density polymer lithium ion battery, the lithium ion battery include positive plate, negative electrode tab, it is porous every
From film and organic electrolyte,
The positive plate includes cobalt acid lithium；
The negative electrode tab includes silicon series composite material；
The porous isolating membrane is aluminum oxide and the mixed painting diaphragm of Kynoar (PVDF)；
The electrolyte is made of lithium salts, carbonic ester, carboxylate and several additives.
Further, cobalt acid lithium D50 is 10~14 μm in the positive plate, specific surface area are as follows: 0.2~0.3m2/g, cobalt acid
Two kinds of elements of lithium doping aluminium and titanium, the mass percentage of aluminium element are 0.05%~0.1%, the mass percentage of titanium elements
It is 0.03~0.07%.
Further, in the negative electrode tab silicon series composite material be silicon oxygen material and graphite material mixing material, wherein
The gram volume of silicon oxygen material is 1500~1700mAh/g, and material particle size D50 is 3~8 μm, and specific surface area is 2~4m2/g；Graphite
The gram volume of material is 340~360mAh/g, and material particle size D50 is 10~15 μm, and specific surface area is 0.7~3m2/g；Mixing material
The gram volume of material is 430~460mAh/g, and mixing material granularity D50 is 10~15 μm, and specific surface area is 0.6~1.5m2/g, silicon
Element mass percentage is 5%~10%, and carbon element content is 90~95%.
Further, the basement membrane of the porous isolating membrane is polyethylene porous membrane, and basement membrane thickness is 5~12 μm, mixes coating
It is the mixture composition of aluminum oxide and Kynoar, coating layer thickness is 3 μm, and mixed coating corresponds to positive pole-face.
Further, lithium salts is LiPF6 in the electrolyte, and the content of lithium salts is 1.0~1.2mol/L；
Carbonic ester, the mass ratio of carboxylate are as follows in the electrolyte:
Ethylene carbonate (EC): propene carbonate (PC): diethyl carbonate (DEC): ethyl methyl carbonate (EMC): propionic acid second
Ester (EP)=20~45:5~20:30~45:0~15:0~15；
Additive level accounts for the 1%~9% of electrolyte gross mass in the electrolyte, and the mass ratio of various additives is such as
Under:
Fluorinated ethylene carbonate (FEC): vinylene carbonate (VC): 1,3- propane sultone (PS): succinonitrile (AN):
Adiponitrile (ADN)=1~9:1~3:0.2~5:0~2:0~2.
Another object of the present invention can be reached by adopting the following technical scheme that:
A kind of preparation method of high energy density polymer lithium ion battery, the lithium ion battery pass through: slurrying-painting
Polymer lithium is made in cloth-roll-in-film-making-winding-assembly-baking-fluid injection-high temperature ageing-- two envelopes of chemical conversion-molding-partial volume process
Ion battery.
Further, the positive plate is obtained by two steps；
First step example cobalt acid lithium in mass ratio: Kynoar (PVDF): carbon nanotube (CNT): carbon black (SP)=94~
97%:1~2%:1~2%:1~2% weighs material requested, obtains anode sizing agent by blender mixing；
First step slurry is coated in aluminum foil current collector by second step, coated face density≤40mg/cm2, roll-in density≤
4.1g/cm3。
Further, the negative electrode tab is obtained by two steps；
First step example silicon series composite material in mass ratio: carboxycellulose sodium (CMC): butadiene-styrene rubber (SBR): carbon black (SP)
=90~96%:1.5~2%:1.5~2.5%:1~2% weighs material requested, obtains negative electrode slurry by blender mixing；
First step slurry is coated in copper foil current collector by second step, coated face density≤20mg/cm2, and roll-in density≤
1.65g/cm3。
Further, the temperature parameter of the high temperature ageing process is 40~60 DEG C, and ageing time is 36~48 hours.
Further, the step of formation process is:
(1) 0.05C charges, time 30min；
(2) 0.1C charges, time 500min, voltage limitation≤4.4V；
(3) 0.2C discharges, time 60min.
The present invention has the following advantages and effects with respect to the prior art:
1, cobalt acid lithium has high voltage, high capacity characteristics, while the use of doped chemical, increases stability of material；
2, silicon series composite material has high capacity characteristics, while its small specific surface product, reduces the generation of side reaction, increases material
The stability of material；
3, isolation film applies diaphragm using aluminum oxide and Kynoar are mixed, and the heat for being conducive to battery molding and battery is steady
It is qualitative；
4, carbonic ester used in organic electrolyte, carboxylate mixing composition have the characteristics that boiling point is high, infiltration is good, are conducive to
High-temperature stability and cycle performance；
5, the composition of additive used in organic electrolyte has the function of anode, cathode film formation protection, and dosage is lower,
Battery impedance is advantageously reduced, cycle performance is conducive to；
6, positive plate and cathode slice prescription are reasonable, advantageously reduce the internal resistance of cell, are conducive to cycle performance；And surface density
It is moderate with compacted density, be conducive to organic electrolyte and sufficiently infiltrate pole piece, is conducive to cycle performance；
7, high temperature ageing temperature and time is conducive to electrolyte and sufficiently infiltrates pole piece, is conducive to cycle performance.
8, chemical synthesis technology is fully charged using low current, is being discharged to half electricity, is being conducive to battery cathode film-forming and negative electrode material
The control of expansion rate.
9, polymer Li-ion battery operating voltage range of the invention is 4.4V~3.0V, and battery cycle life is good, 1C
Charge and discharge normal temperature circulation 500 weeks, 80% or more capacity retention ratio；High temperature and low temperature performance excellent, 55 degree of high temperature discharges, capacity are kept
98% or more rate, the minus 20 degree of electric discharges of low temperature, 60% or more capacity retention ratio.
Detailed description of the invention
Fig. 1 is the process step figure of high energy density polymer preparation method of lithium ion battery disclosed by the invention.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
In following embodiments, high energy density polymer lithium ion battery is disclosed, including positive plate, negative electrode tab, porous
Isolation film and organic electrolyte.Wherein, positive plate mainly contains cobalt acid lithium；Negative electrode tab mainly contains silicon series composite material；Isolation
Film is aluminum oxide and the mixed painting diaphragm of Kynoar；Electrolyte is made of salt, carbonic ester, carboxylate and various additives.
The polymer Li-ion battery operating voltage range is 4.4V~3.0V, and battery cycle life is good, 1C charge and discharge normal temperature circulation 500
Week, 80% or more capacity retention ratio；High temperature and low temperature performance excellent, 55 degree of high temperature discharges, 98% or more capacity retention ratio, low temperature
Minus 20 degree of electric discharges, 60% or more capacity retention ratio.
Embodiment one
The cobalt acid lithium D50 of positive plate is 10~14 μm, specific surface area are as follows: 0.2~0.3m2/g, cobalt acid lithium adulterated al and titanium
Two kinds of elements, the mass percentage of aluminium element are 0.05%~0.1%, the mass percentage of titanium elements is 0.03~
0.07%.
The silicon series composite material of negative electrode tab is the mixing material of silicon oxygen material and graphite.Wherein silicon oxygen material gram volume is
1500~1700mAh/g, material particle size D50 are 3~8 μm, and specific surface area is 2~4m2/g；Graphite material gram volume is 340~
360mAh/g, material particle size D50 are 10~15 μm, and specific surface area is 0.7~3m2/g.After mixing the gram volume of material be 430~
460mAh/g, the D50 of material particle size is 10~15 μm after mixing, specific surface area are as follows: 0.6~1.5m2/g, element silicon quality percentage
Content is 5%~10%, and carbon element content is 90~95%.
The basement membrane of isolation film is polyethylene porous membrane, and basement membrane thickness is 9 μm, and mixed coating is aluminum oxide and polyvinylidene fluoride
The mixture of alkene forms, and coating layer thickness is 3 μm, and coating corresponds to positive pole-face.
Lithium salts is LiPF6 in electrolyte, and the content of lithium salts is 1.1mol/L；
Carbonic ester in electrolyte, carboxylate mass ratio be ethylene carbonate (EC): propene carbonate (PC): carbonic acid
Diethylester (DEC): ethyl methyl carbonate (EMC): ethyl propionate (EP)=20:10:40:15:15；
Additive level accounts for the 8% of electrolyte gross mass in electrolyte, and the mass ratio of various additives is fluoro carbonic acid
Vinyl acetate (FEC): vinylene carbonate (VC): 1,3- propane sultone (PS), succinonitrile (AN): adiponitrile (ADN)=3:
1:1:0.5:1.5.
The lithium ion battery passes through: slurrying-coating-roll-in-film-making-winding-assembly-baking-fluid injection-high temperature ageing-change
Polymer Li-ion battery is made at processes such as-two envelopes-molding-partial volumes.
Wherein, positive plate is obtained by two steps；
First step example cobalt acid lithium in mass ratio: Kynoar (PVDF): carbon nanotube (CNT): carbon black (SP)=96:2:
1:1 weighs material requested, obtains anode sizing agent by blender mixing；
First step slurry is coated in aluminum foil current collector by second step, coated face density 35mg/cm2, roll-in density is
4.1g/cm3。
Wherein, negative electrode tab is obtained by two steps；
First step example silicon series composite material in mass ratio: carboxycellulose sodium (CMC): butadiene-styrene rubber (SBR): carbon black (SP)
=95:1.7:2:1.3 weighs material requested, obtains negative electrode slurry by blender mixing；
First step slurry is coated in copper foil current collector by second step, coated face density 17mg/cm2, roll-in density is
1.65g/cm3。
Wherein, the temperature parameter of high temperature ageing process is 50 DEG C, and ageing time is 36~48 hours.
Wherein, the step of formation process is: (1) 0.05C charges, time 30min；(2) 0.1C charges, time 500min,
Voltage limitation≤4.4V；(3) 0.2C discharges, time 60min.
Embodiment two
The cobalt acid lithium D50 of positive plate is 10~14 μm in the present embodiment, specific surface area are as follows: 0.2~0.3m2/g, cobalt acid lithium
The mass percentage of two kinds of elements of adulterated al and titanium, aluminium element is 0.05%~0.1%, and the mass percentage of titanium elements is
0.03~0.07%.
The silicon series composite material of negative electrode tab is the mixing material of silicon oxygen material and graphite in the present embodiment.Wherein silicon oxygen material
Gram volume is 1500~1700mAh/g, and material particle size D50 is 3~8 μm, and specific surface area is 2~4m2/g；Graphite material gram volume
It is 340~360mAh/g, material particle size D50 is 10~15 μm, and specific surface area is 0.7~3m2/g.The gram volume of material after mixing
It is 430~460mAh/g, the D50 of material particle size is 10~15 μm after mixing, specific surface area are as follows: 0.6~1.5m2/g, element silicon
Mass percentage is 5%~10%, and carbon element content is 90~95%.
The basement membrane of isolation film is polyethylene porous membrane, and basement membrane thickness is 9 μm, and mixed coating is aluminum oxide and polyvinylidene fluoride
The mixture of alkene forms, and coating layer thickness is 3 μm, and coating corresponds to positive pole-face.
Lithium salts is LiPF6 in electrolyte, and the content of lithium salts is 1.1mol/L；
Carbonic ester in electrolyte, carboxylate mass ratio be ethylene carbonate (EC): propene carbonate (PC): carbonic acid
Diethylester (DEC): ethyl methyl carbonate (EMC): ethyl propionate (EP)=30:10:40:5:15；
Additive level accounts for the 8% of electrolyte gross mass in electrolyte, and the mass ratio of various additives is fluoro carbonic acid
Vinyl acetate (FEC): vinylene carbonate (VC): 1,3- propane sultone (PS), succinonitrile (AN): adiponitrile (ADN)=5:
1:1:0.5:1.5.
Above-mentioned lithium ion battery passes through: slurrying-coating-roll-in-film-making-winding-assembly-baking-fluid injection-high temperature ageing-
Polymer Li-ion battery is made in the processes such as chemical conversion-two envelopes-molding-partial volume.
Wherein, positive plate is obtained by two steps；
First step example cobalt acid lithium in mass ratio: Kynoar (PVDF): carbon nanotube (CNT): carbon black (SP)=96:2:
1:1 weighs material requested, obtains anode sizing agent by blender mixing；
First step slurry is coated in aluminum foil current collector by second step, coated face density 35mg/cm2, roll-in density is
4.1g/cm3。
Wherein, negative electrode tab is obtained by two steps；
First step example silicon series composite material in mass ratio: carboxycellulose sodium (CMC): butadiene-styrene rubber (SBR): carbon black (SP)
=95:1.7:2:1.3 weighs material requested, obtains negative electrode slurry by blender mixing；
First step slurry is coated in copper foil current collector by second step, coated face density 17mg/cm2, roll-in density is
1.65g/cm3。
Wherein, the temperature parameter of high temperature ageing process is 50 DEG C, and ageing time is 36~48 hours.
Wherein, the step of formation process is: (1) 0.05C charges, time 30min；(2) 0.1C charges, time 500min,
Voltage limitation≤4.4V；(3) 0.2C discharges, time 60min.
Polymer Li-ion battery prepared by embodiment one and two is tested for the property:
(1) normal temperature circulation is tested: battery being put into 25 ± 3 DEG C of environment, 1C fully charged 4.4V, 1C electric discharge 3.0V, charge and discharge
Circulation 500 times, observes the capacity retention ratio, thickness change and internal resistance change rate of battery.
(2) high temperature discharge is tested: under 25 ± 3 DEG C of environment, 1C electric current shelves battery constant-current discharge to 3.0V 5 minutes, with
1C electric current constant-current constant-voltage charging is to 4.4V, by electric current 0.02C, shelves after five minutes, with 0.5C electric current constant-current discharge to 3.0V,
Recording this discharge capacity is room temperature capacity, then by battery with 1C electric current constant-current constant-voltage charging to 4.4V, by electric current
0.02C.After shelving 2h under the conditions of 55 ± 2 DEG C, with 0.5C current discharge to blanking voltage 3.0V, this discharge capacity is recorded as height
Warm discharge capacity.Experiment terminates, and takes out battery core.
(2) low temperature discharge is tested: under 25 ± 3 DEG C of environment, 1C electric current shelves battery constant-current discharge to 3.0V 5 minutes, with
1C electric current constant-current constant-voltage charging is to 4.4V, by electric current 0.02C, shelves after five minutes, with 0.5C electric current constant-current discharge to 3.0V,
Recording this discharge capacity is room temperature capacity, then by battery with 1C electric current constant-current constant-voltage charging to 4.4V, by electric current
0.02C.After shelving 2h under the conditions of -20 ± 2 DEG C, with 0.2C current discharge to blanking voltage 3.0V, recording this discharge capacity is
High temperature discharge capacity.Experiment terminates, and takes out battery core.
1. normal temperature circulation test result of table
2.55 DEG C of high temperature discharge test results of table
3.-20 DEG C of low temperature discharge test result of table
As known from Table 1, the equal OK of normal temperature circulation test performance of all embodiments, cell thickness change rate is less than 8%, capacity
Normal line of the conservation rate 80% or more, greater than 80%；Cycle performance shows themselves in that embodiment two better than embodiment one.
From table 2 and table 3 it is found that the high temperature discharge test performance OK of all embodiments, the low temperature discharge property of all embodiments
Energy OK, capacity retention ratio is 98% or more；Low temperature performance OK, 60% or more capacity retention ratio.Wherein embodiment one is low
Warm discharge performance is more preferable, and the high temperature discharge performance of embodiment two is more preferable.
This is because DEC and FEC content is higher in the electrolyte of embodiment two.DEC boiling point is higher, is conducive to high-temperature stable
Property；FEC is conducive to cathode film formation.So the cycle performance of battery of embodiment two is more preferable, high-temperature behavior is more preferable, while embodiment
One low temperature performance is more preferable！
After the warm environment storage of of the invention 85 DEG C of polymer Li-ion battery, battery performance keeps normal；In room temperature and 60
Under DEG C hot environment, battery cycle life is good.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of high energy density polymer lithium ion battery, which is characterized in that the lithium ion battery includes positive plate, cathode
Piece, porous isolating membrane and organic electrolyte,
The positive plate includes cobalt acid lithium；
The negative electrode tab includes silicon series composite material；
The porous isolating membrane is aluminum oxide and the mixed painting diaphragm of Kynoar；
The electrolyte is made of lithium salts, carbonic ester, carboxylate and several additives.
2. a kind of high energy density lithium ion lithium ion battery according to claim 1, which is characterized in that the cobalt acid lithium
D50 is 10~14 μm, specific surface area are as follows: 0.2~0.3m2/g, two kinds of elements of cobalt acid lithium adulterated al and titanium, the quality hundred of aluminium element
Dividing content is 0.05%~0.1%, and the mass percentage of titanium elements is 0.03~0.07%.
3. a kind of high energy density lithium ion lithium ion battery according to claim 1, which is characterized in that the negative electrode tab
Middle silicon series composite material is the mixing material of silicon oxygen material and graphite material, wherein the gram volume of silicon oxygen material be 1500~
1700mAh/g, material particle size D50 are 3~8 μm, and specific surface area is 2~4m2/g；The gram volume of graphite material is 340~
360mAh/g, material particle size D50 are 10~15 μm, and specific surface area is 0.7~3m2/g；The gram volume of mixing material is 430~
460mAh/g, mixing material granularity D50 are 10~15 μm, and specific surface area is 0.6~1.5m2/g, element silicon mass percentage
It is 5%~10%, carbon element content is 90~95%.
4. a kind of high energy density lithium ion lithium ion battery according to claim 1, which is characterized in that it is described it is porous every
Basement membrane from film is polyethylene porous membrane, and basement membrane thickness is 5~12 μm, and mixed coating is the mixed of aluminum oxide and Kynoar
Object composition is closed, coating layer thickness is 3 μm, and mixed coating corresponds to positive pole-face.
5. a kind of high energy density lithium ion lithium ion battery according to claim 1, which is characterized in that the electrolyte
Middle lithium salts is LiPF6, and the content of lithium salts is 1.0~1.2mol/L；
Carbonic ester, the mass ratio of carboxylate are as follows in the electrolyte:
Ethylene carbonate: propene carbonate: diethyl carbonate: ethyl methyl carbonate: ethyl propionate=20~45:5~20:30~
45:0~15:0~15；
Additive level accounts for the 1%~9% of electrolyte gross mass in the electrolyte, and the mass ratio of various additives is as follows:
Fluorinated ethylene carbonate: vinylene carbonate: 1,3- propane sultone: succinonitrile: adiponitrile=1~9:1~3:0.2
~5:0~2:0~2.
6. a kind of preparation method of high energy density polymer lithium ion battery, it is characterised in that: the lithium ion battery passes through:
Slurrying-coating-roll-in-film-making-winding-assembly-baking-fluid injection-high temperature ageing-- two envelopes of chemical conversion-molding-partial volume process is made
Polymer Li-ion battery.
7. a kind of high energy density polymer lithium ion battery according to claim 6 and preparation method thereof, feature exists
In the positive plate is obtained by two steps；
First step example cobalt acid lithium in mass ratio: Kynoar (PVDF): carbon nanotube (CNT): carbon black (SP)=94~97%:
1~2%:1~2%:1~2% weighs material requested, obtains anode sizing agent by blender mixing；
First step slurry is coated in aluminum foil current collector by second step, coated face density≤40mg/cm2, roll-in density≤4.1g/
cm3。
8. a kind of high energy density polymer lithium ion battery according to claim 6 and preparation method thereof, feature exists
In the negative electrode tab is obtained by two steps；
First step example silicon series composite material in mass ratio: carboxycellulose sodium (CMC): butadiene-styrene rubber (SBR): carbon black (SP)=90
~96%:1.5~2%:1.5~2.5%:1~2% weighs material requested, obtains negative electrode slurry by blender mixing；
First step slurry is coated in copper foil current collector by second step, coated face density≤20mg/cm2, and roll-in density≤
1.65g/cm3。
9. a kind of high energy density polymer lithium ion battery according to claim 6 and preparation method thereof, feature exists
In the temperature parameter of the high temperature ageing process is 40~60 DEG C, and ageing time is 36~48 hours.
10. a kind of high energy density polymer lithium ion battery according to claim 6 and preparation method thereof, feature exists
It is in the step of, formation process:
(1) 0.05C charges, time 30min；
(2) 0.1C charges, time 500min, voltage limitation≤4.4V；
(3) 0.2C discharges, time 60min.
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