CN106653377B - A kind of big multiplying power hybrid battery capacitor and preparation method thereof - Google Patents
A kind of big multiplying power hybrid battery capacitor and preparation method thereof Download PDFInfo
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- CN106653377B CN106653377B CN201611158154.9A CN201611158154A CN106653377B CN 106653377 B CN106653377 B CN 106653377B CN 201611158154 A CN201611158154 A CN 201611158154A CN 106653377 B CN106653377 B CN 106653377B
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Abstract
Big multiplying power hybrid battery capacitor disclosed by the invention and preparation method thereof, including the electrolyte and battery core in shell and shell, in which: battery core is mainly assembled by positive plate, diaphragm and negative electrode tab overlapping；Positive plate includes collector and the positive electrode for being formed in collection liquid surface, and positive electrode includes the composite material of NCA, LFP, AC；Negative electrode tab includes collector and the negative electrode material for being formed in collection liquid surface, and negative electrode material includes one or more of AGP, CNT, AC.The present invention program effectively improves electrode material and solvent compatibility problem, and the low problem of charging and discharging capabilities meets the needs of large current density to significantly improve the high rate performance of product caused by improvement electrode material is excessively high to the sensibility of electrolyte.
Description
Technical field
The present invention relates to a kind of battery capacitor and preparation method thereof, especially a kind of big multiplying power hybrid battery capacitor and its system
Preparation Method.
The meaning of following expression formula in the present invention are as follows:
NCA:LiNi0.8Co0.15Al0.05O2
LFP:LiFePO4
AGP: graphite
CNT: carbon nanotube
AC: active carbon
Background technique
Mainly there are lithium ion battery and supercapacitor during common energy storage at present, lithium ion battery has high-energy density
The characteristics of, service life cycle is short, power density is low, although supercapacitor specific power and cycle life are high, but energy
Density is low, therefore is badly in need of developing a kind of mixed type energy storage device for having both high power density and high-energy density.
Super capacitance cell is a kind of new type of energy storage device for having both high-energy density and high power density, it mainly passes through
Electric double layer capacitance and embedding/de- two ways of lithium ion carry out " difunctional " energy storage, develop the high-performance with " difunctional " feature
Energy storage device is significant.In the popular several positive electrodes studied at present, LiNi0.8Co0.15Al0.05O2(hereinafter referred to as
NCA) positive electrode is provided simultaneously with the advantages that high capacity and long-life.The gram volume of material is up to 185mAh/g, compared to conventional cobalt
The battery of sour lithium system can be improved 20%~40%, in numerous positive electrodes, LiFePO4(hereinafter referred to as LFP) material tool
There is optimal security performance, the olivine-type structure of LFP makes material also have extraordinary stability under the conditions of unconventional,
The addition of LFP can reduce the heat generated in charge and discharge process, improve the cycle performance of mixing material.Graphite is as cathode
(hereinafter referred to as AGP) has good charge and discharge level platform, and voltage is steady.But due to the crystallinity of graphite height, there is height to take
To layer structure, more sensitive to electrolyte, poor with solvent compatibility, high current charge-discharge ability is low, the high rate performance of product
Difference, it is difficult to meet the needs of large current density.
Summary of the invention
To solve the above problems, the invention discloses a kind of big multiplying power hybrid battery capacitors and preparation method thereof, by right
The selection and combination of electrode material improve electrode material pair to effectively improve electrode material and solvent compatibility problem
The low problem of charging and discharging capabilities caused by the sensibility of electrolyte is excessively high, so that the high rate performance of product is significantly improved, it is full
The foot needs of large current density.
Big multiplying power hybrid battery capacitor disclosed by the invention, including the electrolyte and battery core in shell and shell,
In:
Battery core is mainly assembled by positive plate, diaphragm and negative electrode tab overlapping；
Positive plate includes collector and the positive electrode for being formed in collection liquid surface, and positive electrode includes NCA, LFP, AC
Composite material；
Negative electrode tab includes collector and the negative electrode material for being formed in collection liquid surface, and negative electrode material includes AGP, CNT, AC
One or more of.Preferably, collector is corrosive aluminum foil.
A kind of improvement of big multiplying power hybrid battery capacitor disclosed by the invention, positive electrode includes following mass percent:
AC:4-6%, binder 5-8%, conductive agent 3-8%, NCA-LFP material: surplus.
A kind of improvement of big multiplying power hybrid battery capacitor disclosed by the invention, the composition of NCA-LFP material in positive electrode
Are as follows: the mass ratio of NCA and LFP is (0.1~9): 1.
A kind of improvement of big multiplying power hybrid battery capacitor disclosed by the invention, negative electrode material includes following mass percent:
AC:3-8%, binder 5-8%, conductive agent 3-8%, AGP-CNT material: surplus.
A kind of improvement of big multiplying power hybrid battery capacitor disclosed by the invention, the composition of AGP-CNT material in negative electrode material
Are as follows: the mass ratio of AGP and CNT is 1:(0.001~0.15).
A kind of improvement of big multiplying power hybrid battery capacitor disclosed by the invention, conductive agent is conductive carbon black, graphene, carbon are received
It is one or more of in mitron, Ketjen black.
A kind of improvement of big multiplying power hybrid battery capacitor disclosed by the invention, binder are Kynoar, polytetrafluoroethyl-ne
It is one or more of in alkene, butadiene-styrene rubber.
The preparation method of big multiplying power hybrid battery capacitor disclosed by the invention, including positive plate preparation, negative electrode tab preparation,
Middle positive plate preparation includes anode sizing agent preparation, positive plate compacting, and wherein anode sizing agent preparation is uniform with solvent by positive electrode
It is mixed to get anode sizing agent, positive plate is compressed to the two sides that the coated equipment of anode sizing agent uniformly makes coating be coated in collector
On, positive electrode that slurry is formed on a current collector it is unilateral with a thickness of 90-150 μm (referring to thickness unilateral on a current collector),
And with 1.5-2.0g/cm3The density of size rolls, is punched anode pole piece is made.
A kind of improvement of the preparation method of big multiplying power hybrid battery capacitor disclosed by the invention, negative electrode tab preparation include cathode
Slurry preparation, negative electrode tab compacting, wherein negative electrode slurry preparation is uniformly mixed to get negative electrode slurry, cathode by negative electrode material and solvent
Piece, which is compressed to the coated equipment of negative electrode slurry, is coated in coating uniform on the two sides of collector, what slurry was formed on a current collector
Negative electrode material with a thickness of 90-150 μm (refer on a current collector unilateral thickness), and with 1.2-1.8g/cm3The density of size is ground
Cathode pole piece is made in pressure, punching.
In order to achieve the purpose that foregoing invention, the invention adopts the following technical scheme:
One kind (NCA-LFP-AC)/(AGP-CNT-AC) hybrid battery capacitor, including the electrolyte in shell and shell
And battery core, battery core are mainly assembled by positive plate, diaphragm and negative electrode tab overlapping, main the answering with NCA, LFP, AC of capacitor batteries
Condensation material is positive electrode, is mainly negative electrode material with one or more of AGP, CNT, AC.
Preferably, the present invention uses to meet the needs of different electric appliances using the mixture of NCA, LFP, AC as electricity
The positive electrode of pond capacitor, the positive electrodes such as NCA, LFP of utility complementation carry out ultrasonic disperse physical mixed, improve NCA
At high charge state (SOC), the problem of poor safety performance, while its high rate performance is improved, and is applied to battery capacitor of the present invention
In obtain good effect.
Preferably, using the negative electrode material using the mixture of AGP, CNT, AC as battery capacitor, utility is complementary
The positive electrodes such as AGP, CNT, AC carry out ultrasonic disperse physical mixed, improve AGP and solvent compatibility be poor, high current charge-discharge
The low problem of ability, and be applied to obtain good effect in battery capacitor of the present invention.The mixing of positive and negative electrode material of the present invention
It is coated different from chemistry, preparation process does not chemically react, and can reduce cost while improving material single performance, be convenient for
Engineering application.
Preferably, the present invention controls positive theoretical capacity by changing the quality of NCA and LFP.Positive electrode includes
Following mass percent: AC:4-6%, binder 5-8%, conductive agent 3-8%, NCA-LFP: surplus.Further preferably, NCA and
The mass ratio of LFP is (0.1~9): 1.
Preferably, the present invention controls positive theoretical capacity by changing the quality of NCA and LFP.Negative electrode material includes
Following mass percent: AC:3-8%, binder 5-8%, conductive agent 3-8%, AGP-CNT: surplus.Further preferably, AGP and
The mass ratio of CNT is 1:(0.001~0.15).
Preferably, conductive agent is conductive carbon black, graphene, carbon nanotube or Ketjen black.
Preferably, binder be Kynoar, polytetrafluoroethylene (PTFE) or butadiene-styrene rubber.
Preferably, the solute of electrolyte is lithium perchlorate, hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate, trifluoro
At least one of methane sulfonic acid lithium, tetraethylammonium tetrafluoroborate salt；
The solvent of electrolyte is acetonitrile, ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid first
One of ethyl ester is several；
The additive of electrolyte is di-oxalate lithium borate, dimethyl acetamide, three (five fluorinated phenyls) boron, tripotassium phosphate
One or more of ester, triphenyl phosphate, phenodiazine phenyl ketone.
Preferably, diaphragm is microporous polypropylene membrane, a kind of in polyethene microporous membrane, composite membrane, paper diaphragm.
Preferably, the coated equipment of anode sizing agent is coated in coating on the two sides of corrosive aluminum foil, positive electrode
90-150 μm of thickness (refer on a current collector unilateral thickness), with 1.5-2.0g/cm3The density of size rolls, is punched and is made
Anode pole piece.
Preferably, the coated equipment of negative electrode slurry is coated in coating uniform on the two sides of corrosive aluminum foil, negative electrode material
90-150 μm of thickness (refer on a current collector unilateral thickness), with 1.2-1.8g/cm3The density of size rolls, is punched and is made
Cathode pole piece.
Preferably, carrying out the matching of electrode according to the mass ratio of positive and negative electrode electrode active material 1:1-1:2, use
The mode of " Z " type lamination makes battery core, obtains novel mixing capacitor batteries after drying, encapsulation fluid injection.
In the present invention program, the corrosive aluminum foil surface as collector is also formed with aluminium amalgam.Preferably, corrosive aluminum foil table
The aluminium amalgam in face is orientated on the surface.Preferably, the length of the protrusion part of the aluminium amalgam on corrosive aluminum foil surface is 0.01-
0.03mm.In corrosive aluminum foil external coating mercury salt solution, to realize the formation of iron amalgam, while by solution concentration and ring
Border temperature is to realize orientation.In the program by using surface growth aluminium amalgam, to improve Surface binding energy power, with
Its solid-state enhancing structure grown is fallen off performance to promote anti-corrosion, is extended thus the binding performance between improving pole piece structure
The service life of product, and improve electric conductivity.Enhance transition structure additionally by the aluminium amalgam using appropriate protrusion length,
Protrusion is in the specific length of aluminium foil surface, to form " pinning " appropriate between pole piece structure, and by the length
Control, avoid it is too short and " pinning " effect is unobvious, it is not significant and influence product to link enhancement effect between the two
Performance, while avoiding too long to form larger torque but protruding portion on boundary in prominent interface when using too long middle stress
It is broken at face, to influence whole service performance, be thus under this length has fabulous combination between the two
Reinforcing property, and the corrosion-resistant anti-dropout stripping performance of reinforcing material, and improve the electric conductivity of pole piece.
Compared with prior art, the present invention beneficial effect is:
1. (NCA-LFP-AC)/(AGP-CNT-AC) hybrid battery capacitor of the invention has big multiplying power, long-life, great Rong
The cheap advantage of amount, safety.
2. positive electrode of the anode of the invention using the mixture of NCA, LFP, AC as battery capacitor, utility are complementary
The positive electrodes such as NCA, LFP carry out ultrasonic disperse physical mixed, improve NCA at high charge state (SOC), poor safety performance
Problem, while its high rate performance is improved, and be applied to obtain good effect in battery capacitor of the present invention.
4. cathode of the present invention uses ultrasonic disperse mixing method, by the graphite of reversible embedding de- lithium capacity with higher, have
The carbon nanotube of high circulation performance and active carbon with excellent electrochemical stability carry out physical mixed, and process is simple, quickly
Efficiently, and good conductive network can be constructed.The conduction of electrode material is greatly promoted by the introducing of carbon nanotube and active carbon
The characteristic of performance and partition capacitance energy storage significantly improves the high rate performance of product, meets the needs of large current density.
5. the mixing of positive and negative electrode material of the present invention is different from chemistry cladding, preparation process is not chemically reacted, and is improved
Cost can be reduced while material single performance, convenient for engineering application.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated, it should be understood that following specific embodiments are only used for
It is bright the present invention rather than limit the scope of the invention.
Specific embodiment 1:
It prepares anode pole piece: being first in mass ratio the ratio of 9:1 by positive electrode active materials NCA and LFP, it is enterprising in ball mill
Row mixing 4 hours, is subsequently placed in ultrasonic oscillator (220V, 50Hz) and carries out ultrasonic mixing, solvent is dehydrated alcohol, and liquid is solid
It is 8:2 than control, incorporation time is 30 minutes, dries 4h at 140 DEG C of vacuum then to get anode composite material.
Then by positive electrode active materials, active carbon, conductive agent (SuperP+ Ketjen black), binder (PVDF) according to quality
Ratio than 72:18:5:5 is dissolved in N-methyl pyrrolidones after weighing, and it is small to stir 4 under vacuum using high-speed mixing equipment
When form uniform sizing material, high-speed stirred forms anode sizing agent.Coated equipment uniformly makes two sides of the coating coated in corrosive aluminum foil
On, with 1.8g/cm after row order of going forward side by side ladder type is dry3The density of size rolls, subsequent big multiplying power long-life high-power battery capacitor
Anode pole piece preparation is completed.
Prepare cathode pole piece: first that negative electrode active material graphite, carbon nanotube is enterprising in ball mill according to the ratio of 1:0.1
Row mixing 4 hours, is subsequently placed in ultrasonic oscillator (220V, 50Hz) and carries out ultrasonic mixing, solvent is dehydrated alcohol, and liquid is solid
It is 8:2 than control, incorporation time is 30 minutes, dries 4h at 140 DEG C of vacuum then to get graphite/carbon nanotube composite
Material.
By negative electrode active material, conductive agent (SuperP), binder (40%SBR), dispersing agent (2%CMC) according to quality
Ratio than 87:5:5:2.5 is dissolved in deionized water after weighing, and stirs 4 hours shapes under vacuum using high-speed mixing equipment
It at uniform sizing material, is evenly applied on the two sides of corrosive aluminum foil using coating equipment, it is dry to carry out staged while coating, does
Dry complete electrode is with 1.6g/cm3Density roll, then prepared by big multiplying power long-life high-power battery capacitor cathode pole piece
At.
The diaphragm for the use of U.S.'s Celgard company model being C480, electrolyte use 1M LiPF6It is molten with 0.5M SBP
Matter, using EC, DEC, DMC of volume ratio 1:1:1 as solvent.By certain thickness with the positive and negative electrode active material of 1.5:1 than matching
Positive and negative electrode pole piece is separated using diaphragm and battery core is made by positive and negative electrode pole piece, and the drying 24 hours of 80 DEG C of vacuum is infused in glove box
Electrolyte post package carries out chemical conversion and secondary encapsulation after standing 12h, obtains capacitor batteries in aluminum plastic film.It is tested in 2C electricity
Constant current charge and discharge test is carried out under current density, it is 102Wh/Kg that the specific energy of battery capacitor, which reaches, after 20000 circulations, capacity
Conservation rate has 83%.
Battery capacitor embodiment
In the present embodiment, big multiplying power hybrid battery capacitor, including the electrolyte and battery core in shell and shell, in which:
Battery core is mainly assembled by positive plate, diaphragm and negative electrode tab overlapping；Positive plate includes collector and is formed in afflux body surface
The positive electrode in face, positive electrode include the composite material of NCA, LFP, AC；Negative electrode tab includes collector and is formed in afflux
The negative electrode material in body surface face, negative electrode material include one or more of AGP, CNT, AC；
Negative electrode material can be any for including following situation: AGP in this embodiment scheme；CNT；AC；AGP,CNT；AC,
AGP；CNT,AC；AGP,CNT,AC.It is only (identical parameter feelings when being distinguished shown in this prescription case with aforementioned embodiment difference
Shape is excluded), battery capacitor sample tests it and carries out constant current charge and discharge test, the ratio energy of battery capacitor under 2C current density
Amount is greater than 85Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 80%.
It is distinguished with above-described embodiment, positive electrode includes following mass percent: (AC contains AC:4% in positive electrode
Amount can also be include but not limited to following any: 4.1wt%, 4.2wt%, 4.3wt%, 4.4wt%, 4.5wt%,
4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5.0wt%, 5.1wt%, 5.2wt%, 5.3wt%, 5.4wt%,
It is other any within the scope of 5.5wt%, 5.6wt%, 5.7wt%, 5.8wt%, 5.9wt%, 6.0wt% and 4-6wt%
Value), binder 5-8% (it includes but not limited to following any for being bonded agent content in positive electrode can also be: 5.1wt%,
5.2wt%, 5.3wt%, 5.4wt%, 5.5wt%, 5.6wt%, 5.7wt%, 5.8wt%, 5.9wt%, 6.0wt%,
6.1wt%, 6.2wt%, 6.3wt%, 6.4wt%, 6.5wt%, 6.6wt%, 6.7wt%, 6.8wt%, 6.9wt%,
7.0wt%, 7.1wt%, 7.2wt%, 7.3wt%, 7.4wt%, 7.5wt%, 7.6wt%, 7.7wt%, 7.8wt%,
Other arbitrary values within the scope of 7.9wt%, 8.0wt% and 5-8wt%), (conductive agent content in positive electrode of conductive agent 3%
It includes but not limited to following any for can also being: 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%,
3.7wt%, 3.8wt%, 3.9wt%, 4.0wt%, 4.1wt%, 4.2wt%, 4.3wt%, 4.4wt%, 4.5wt%,
4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5.0wt%, 5.1wt%, 5.2wt%, 5.3wt%, 5.4wt%,
5.5wt%, 5.6wt%, 5.7wt%, 5.8wt%, 5.9wt%, 6.0wt%, 6.1wt%, 6.2wt%, 6.3wt%,
6.4wt%, 6.5wt%, 6.6wt%, 6.7wt%, 6.8wt%, 6.9wt%, 7.0wt%, 7.1wt%, 7.2wt%,
7.3wt%, 7.4wt%, 7.5wt%, 7.6wt%, 7.7wt%, 7.8wt%, 7.9wt%, 8.0wt% and 3-8wt% model
Enclose interior other arbitrary values), NCA-LFP material: surplus.It is only when being distinguished shown in this prescription case with aforementioned embodiment difference
(identical parameter situation is excluded), battery capacitor sample test it and carry out constant current charge and discharge test under 2C current density, electricity
The specific energy of pond capacitor is greater than 86Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 82%.
It is distinguished with above-described embodiment, the composition of NCA-LFP material in positive electrode are as follows: the mass ratio of NCA and LFP is
0.1:1 (mass ratio of NCA and LFP can also be include but not limited to following any: 0.2:1,0.3:1,0.4:1,0.5:1,
0.6:1,0.7:1,0.8:1,0.9:1,1.0:1,1.1:1,1.2:1,1.3:1,1.4:1,1.5:1,1.6:1,1.7:1,1.8:
1,1.9:1,2.0:1,2.1:1,2.2:1,2.3:1,2.4:1,2.5:1,2.6:1,2.7:1,2.8:1,2.9:1,3.0:1,
3.1:1,3.2:1,3.3:1,3.4:1,3.5:1,3.6:1,3.7:1,3.8:1,3.9:1,4.0:1,4.1:1,4.2:1,4.3:
1,4.4:1,4.5:1,4.6:1,4.7:1,4.8:1,4.9:1,5.0:1,5.1:1,5.2:1,5.3:1,5.4:1,5.5:1,
5.6:1,5.7:1,5.8:1,5.9:1,6.0:1,6.1:1,6.2:1,6.3:1,6.4:1,6.5:1,6.6:1,6.7:1,6.8:
1,6.9:1,7.0:1,7.1:1,7.2:1,7.3:1,7.4:1,7.5:1,7.6:1,7.7:1,7.8:1,7.9:1,8.0:1,
8.1:1,8.2:1,8.3:1,8.4:1,8.5:1,8.6:1,8.7:1,8.8:1,8.9:1,9.0:1 and (0.1~9): 1 range
Interior other arbitrary values).It is only that (identical parameter situation gives when distinguishing shown in this prescription case with aforementioned embodiment difference
Exclude), battery capacitor sample tests it and carries out constant current charge and discharge test under 2C current density, and the specific energy of battery capacitor is greater than
87Wh/Kg, after 20000 circulations, capacity retention ratio is not less than 84%.
It is distinguished with above-described embodiment, negative electrode material includes following mass percent: (AC contains AC:3% in negative electrode material
Amount can also be include but not limited to following any: 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%,
3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, 4.0wt%, 4.1wt%, 4.2wt%, 4.3wt%, 4.4wt%,
4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5.0wt%, 5.1wt%, 5.2wt%, 5.3wt%,
5.4wt%, 5.5wt%, 5.6wt%, 5.7wt%, 5.8wt%, 5.9wt%, 6.0wt%, 6.1wt%, 6.2wt%,
6.3wt%, 6.4wt%, 6.5wt%, 6.6wt%, 6.7wt%, 6.8wt%, 6.9wt%, 7.0wt%, 7.1wt%,
7.2wt%, 7.3wt%, 7.4wt%, 7.5wt%, 7.6wt%, 7.7wt%, 7.8wt%, 7.9wt%, 8.0wt% and 3-
Other arbitrary values within the scope of 8wt%), binder 5% (in negative electrode material be bonded agent content can also be include but not limited to as
Under it is any: 5.1wt%, 5.2wt%, 5.3wt%, 5.4wt%, 5.5wt%, 5.6wt%, 5.7wt%, 5.8wt%,
5.9wt%, 6.0wt%, 6.1wt%, 6.2wt%, 6.3wt%, 6.4wt%, 6.5wt%, 6.6wt%, 6.7wt%,
6.8wt%, 6.9wt%, 7.0wt%, 7.1wt%, 7.2wt%, 7.3wt%, 7.4wt%, 7.5wt%, 7.6wt%,
Other arbitrary values within the scope of 7.7wt%, 7.8wt%, 7.9wt%, 8.0wt% and 5-8wt%), 3% (cathode of conductive agent
In material conductive agent content can also be include but not limited to following any: 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%,
3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, 4.0wt%, 4.1wt%, 4.2wt%, 4.3wt%,
4.4wt%, 4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5.0wt%, 5.1wt%, 5.2wt%,
5.3wt%, 5.4wt%, 5.5wt%, 5.6wt%, 5.7wt%, 5.8wt%, 5.9wt%, 6.0wt%, 6.1wt%,
6.2wt%, 6.3wt%, 6.4wt%, 6.5wt%, 6.6wt%, 6.7wt%, 6.8wt%, 6.9wt%, 7.0wt%,
7.1wt%, 7.2wt%, 7.3wt%, 7.4wt%, 7.5wt%, 7.6wt%, 7.7wt%, 7.8wt%, 7.9wt%,
Other arbitrary values within the scope of 8.0wt% and 3-8wt%), AGP-CNT material: surplus.Only with aforementioned embodiment difference
When to distinguish shown in this prescription case (identical parameter situation is excluded), battery capacitor sample tests it in 2C current density
The specific energy of lower progress constant current charge and discharge test, battery capacitor is greater than 872Wh/Kg, after 20000 circulations, capacity retention ratio
It is not less than 84%.
It is distinguished with above-described embodiment, the composition of AGP-CNT material in negative electrode material are as follows: the mass ratio of AGP and CNT is
1:0.001 (mass ratio of AGP and CNT can also be include but not limited to following any: 1:0.002,1:0.003,1:0.004,
1:0.005,1:0.006,1:0.007,1:0.008,1:0.009,1:0.01,1:0.02,1:0.03,1:0.04,1:0.05,1:
0.06,1:0.07,1:0.08,1:0.09,1:0.1,1:0.11,1:0.12,1:0.13,1:0.14,1:0.15 and 1:
Other arbitrary values in (0.001~0.15) range).It is only when being distinguished shown in this prescription case with aforementioned embodiment difference
(identical parameter situation is excluded), battery capacitor sample test it and carry out constant current charge and discharge test under 2C current density, electricity
The specific energy of pond capacitor is greater than 88Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 86%.
It is distinguished with above-described embodiment, conductive agent can be any for including but not limited to following situation: conductive carbon black；
Graphene；Carbon nanotube；Ketjen black；Conductive carbon black, graphene；Carbon nanotube, Ketjen black；Graphene, carbon nanotube；Conductive carbon
Black, Ketjen black；Conductive carbon black, graphene, carbon nanotube；Ketjen black, conductive carbon black, graphene；Carbon nanotube, is led at Ketjen black
Electrical carbon is black；；Conductive carbon black, graphene, carbon nanotube, Ketjen black.It is only shown in this prescription case with aforementioned embodiment difference
(identical parameter situation is excluded), battery capacitor sample when difference, test it and carry out constant current charge and discharge under 2C current density
The specific energy of test, battery capacitor is greater than 89Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 86%.
It is distinguished with above-described embodiment, binder can be any for including but not limited to following situation: polyvinylidene fluoride
Alkene；Polytetrafluoroethylene (PTFE)；Butadiene-styrene rubber；Kynoar, polytetrafluoroethylene (PTFE)；Butadiene-styrene rubber, Kynoar；Polytetrafluoroethylene (PTFE),
Butadiene-styrene rubber；Kynoar, polytetrafluoroethylene (PTFE), butadiene-styrene rubber.It is only shown in this prescription case with aforementioned embodiment difference
(identical parameter situation is excluded), battery capacitor sample when difference, test it and carry out constant current charge and discharge under 2C current density
The specific energy of test, battery capacitor is greater than 90Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 87%.
It is distinguished with above-described embodiment, the solute of electrolyte can be any for including but not limited to following situation: high
Lithium chlorate；Hexafluoroarsenate lithium；LiBF4；Lithium hexafluoro phosphate；Trifluoromethyl sulfonic acid lithium；Tetraethylammonium tetrafluoroborate salt；It is high
Lithium chlorate, hexafluoroarsenate lithium；LiBF4, lithium hexafluoro phosphate；Trifluoromethyl sulfonic acid lithium, tetraethylammonium tetrafluoroborate salt；It is high
Lithium chlorate, hexafluoroarsenate lithium, LiBF4；Lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, tetraethylammonium tetrafluoroborate salt；It is high
Lithium chlorate, hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate；Trifluoromethyl sulfonic acid lithium, tetraethylammonium tetrafluoroborate salt, height
Lithium chlorate, hexafluoroarsenate lithium；LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium, tetraethylammonium tetrafluoroborate salt；It is high
Lithium chlorate, hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium；Tetraethylammonium tetrafluoroborate salt, height
Lithium chlorate, hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate；Trifluoromethyl sulfonic acid lithium, tetraethylammonium tetrafluoroborate salt, height
Lithium chlorate, hexafluoroarsenate lithium, LiBF4；Lithium perchlorate, hexafluoroarsenate lithium, LiBF4, lithium hexafluoro phosphate, fluoroform
Base Sulfonic Lithium, tetraethylammonium tetrafluoroborate salt.It is (identical when only being distinguished shown in this prescription case with aforementioned embodiment difference
Parameter situation is excluded), battery capacitor sample tests it and carries out constant current charge and discharge test, battery capacitor under 2C current density
Specific energy be greater than 92Wh/Kg, by 20000 times circulation after, capacity retention ratio is not less than 87%.
It is distinguished with above-described embodiment, the solvent of electrolyte can be any for including but not limited to following situation: second
Nitrile；Ethylene carbonate；Propene carbonate；Dimethyl carbonate；Diethyl carbonate；Methyl ethyl carbonate；Acetonitrile, ethylene carbonate；Carbon
Acid propylene ester, dimethyl carbonate；Diethyl carbonate, methyl ethyl carbonate；Acetonitrile, ethylene carbonate, propene carbonate；Carbonic acid diformazan
Ester, diethyl carbonate, methyl ethyl carbonate；Acetonitrile, ethylene carbonate, propene carbonate, dimethyl carbonate；Diethyl carbonate, carbon
Sour methyl ethyl ester, acetonitrile, ethylene carbonate；Propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate；Acetonitrile, carbon
Vinyl acetate, propene carbonate, dimethyl carbonate, diethyl carbonate；Methyl ethyl carbonate, acetonitrile, ethylene carbonate, propylene carbonate
Ester, dimethyl carbonate；Diethyl carbonate, methyl ethyl carbonate, acetonitrile, ethylene carbonate, propene carbonate；Acetonitrile, ethylene carbonate
Ester, propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate.It is only this prescription with aforementioned embodiment difference
Shown in case when difference (identical parameter situation is excluded), battery capacitor sample tests it and carries out perseverance under 2C current density
Charge and discharge test is flowed, the specific energy of battery capacitor, which reaches, is greater than 93Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than
88%.
It is distinguished with above-described embodiment, the additive of electrolyte can be any for including but not limited to following situation:
Di-oxalate lithium borate；Dimethyl acetamide；Three (five fluorinated phenyls) boron；Trimethyl phosphate；Triphenyl phosphate；Phenodiazine phenyl ketone；
Di-oxalate lithium borate, dimethyl acetamide；Three (five fluorinated phenyls) boron, trimethyl phosphate；Triphenyl phosphate, phenodiazine phenyl ketone；
Di-oxalate lithium borate, dimethyl acetamide, three (five fluorinated phenyls) boron；Trimethyl phosphate, triphenyl phosphate, phenodiazine phenyl ketone；
Di-oxalate lithium borate, dimethyl acetamide, three (five fluorinated phenyls) boron, trimethyl phosphate；Triphenyl phosphate, phenodiazine phenyl ketone,
Di-oxalate lithium borate, dimethyl acetamide；Three (five fluorinated phenyls) boron, trimethyl phosphate, triphenyl phosphate, phenodiazine phenyl ketone；
Di-oxalate lithium borate, dimethyl acetamide, three (five fluorinated phenyls) boron, trimethyl phosphate, triphenyl phosphate；Phenodiazine phenyl ketone,
Di-oxalate lithium borate, dimethyl acetamide, three (five fluorinated phenyls) boron, trimethyl phosphate；Triphenyl phosphate, phenodiazine phenyl ketone,
Di-oxalate lithium borate, dimethyl acetamide, three (five fluorinated phenyls) boron；Di-oxalate lithium borate, dimethyl acetamide, three (five fluorine
Change phenyl) boron, trimethyl phosphate, triphenyl phosphate, phenodiazine phenyl ketone.It is only this prescription case institute with aforementioned embodiment difference
Show (identical parameter situation is excluded), battery capacitor sample when difference, tests it and carry out constant current under 2C current density and fill
Test is put, the specific energy of battery capacitor is greater than 93Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 89%.
It is distinguished with above-described embodiment, diaphragm can be any for including but not limited to following situation: polypropylene microporous
Film；Polyethene microporous membrane；Composite membrane；Paper diaphragm.It is (identical when only being distinguished shown in this prescription case with aforementioned embodiment difference
Parameter situation excluded), battery capacitor sample tests it and carries out constant current charge and discharge test under 2C current density, battery electricity
The specific energy of appearance is greater than 94Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 88%.
It is distinguished with above-described embodiment, the coated equipment of anode sizing agent uniformly makes two sides of the coating coated in corrosive aluminum foil
On, positive electrode unilateral 90 μm of thickness (positive electrode can also be in unilateral thickness include but not limited to following any:
91、92、93、94、95、96、97、98、99、100、101、102、103、104、105、106、107、108、109、110、111、
112、113、114、115、116、117、118、119、120、121、122、123、124、125、126、127、128、129、130、
131、132、133、134、135、136、137、138、139、140、141、142、143、144、145、146、147、148、149、
Other arbitrary values in 150 μm and 90-150 μ m), with 1.5g/cm3The density of size rolls that (rolling density can be with
To include but not limited to following any: 1.6g/cm3、1.7g/cm3、1.8g/cm3、1.9g/cm3、2.0g/cm3And 1.5-
2.0g/cm3Other arbitrary values in range), punching anode pole piece is made.It is only this prescription case with aforementioned embodiment difference
(identical parameter situation is excluded), battery capacitor sample test it and carry out constant current under 2C current density when shown difference
The specific energy of charge and discharge test, battery capacitor is greater than 96Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than
85%.
It is distinguished with above-described embodiment, the coated equipment of negative electrode slurry makes two sides of the coating uniform coated in corrosive aluminum foil
On, 90 μm of the thickness of negative electrode material (negative electrode material can also be in unilateral thickness include but not limited to following any: 91,92,
93、94、95、96、97、98、99、100、101、102、103、104、105、106、107、108、109、110、111、112、113、
114、115、116、117、118、119、120、121、122、123、124、125、126、127、128、129、130、131、132、
133,134,135,136,137,138,139,140,141,142,143,144,145,146,147,148,149,150 μm and
Other arbitrary values in 90-150 μ m), with 1.2g/cm3The density of size rolls that (rolling density can also be to include without
It is limited to following any: 1.3g/cm3、1.4g/cm3、1.5g/cm3、1.6g/cm3、1.7g/cm3、1.8g/cm3And 1.2-1.8g/
cm3Other arbitrary values in range), punching cathode pole piece is made.It is only shown in this prescription case with aforementioned embodiment difference
(identical parameter situation is excluded), battery capacitor sample when difference, test it and carry out constant current charge and discharge under 2C current density
The specific energy of test, battery capacitor is greater than 96Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 87%.
It is distinguished with above-described embodiment, according to the mass ratio of positive and negative electrode electrode active material 1:1, (battery capacitor is just
It includes but not limited to following any that the active material of negative electrode, which assembles ratio and can also be: 1:1.1,1:1.2,1:1.3,1:1.4,
Other arbitrary values within the scope of 1:1.5,1:1.6,1:1.7,1:1.8,1:1.9,1:2 and 1:1-1:2) carry out electrode
Match, make battery core by the way of " Z " type lamination, obtains novel mixing capacitor batteries after drying, encapsulation fluid injection.With aforementioned tool
When the difference of body embodiment is only difference shown in this prescription case (identical parameter situation is excluded), battery capacitor sample, test
It carries out constant current charge and discharge test under 2C current density, and the specific energy of battery capacitor is greater than 97Wh/Kg, recycles by 20000 times
Afterwards, capacity retention ratio is not less than 88%.
Prepare embodiment 1
The preparation method of big multiplying power hybrid battery capacitor in the present embodiment, including positive plate preparation, negative electrode tab preparation, wherein
Positive plate preparation includes anode sizing agent preparation, positive plate compacting, and wherein anode sizing agent preparation is uniformly mixed by positive electrode with solvent
Conjunction obtains anode sizing agent, and positive plate, which is compressed to the coated equipment of anode sizing agent, is coated in coating on the two sides of collector,
(positive electrode can also be to include in unilateral thickness with a thickness of 90 μm for the positive electrode that slurry is formed on a current collector unilateral
And be not limited to following any: 91,92,93,94,95,96,97,98,99,100,101,102,103,104,105,106,107,
108、109、110、111、112、113、114、115、116、117、118、119、120、121、122、123、124、125、126、
127、128、129、130、131、132、133、134、135、136、137、138、139、140、141、142、143、144、145、
146, other arbitrary values in 147,148,149,150 μm and 90-150 μ m), and with 1.5g/cm3The density of size is ground
(it includes but not limited to following any for rolling density can also be to pressure: 1.6g/cm3、1.7g/cm3、1.8g/cm3、1.9g/cm3、
2.0g/cm3And 1.5-2.0g/cm3Other arbitrary values in range), punching anode pole piece is made.
It is distinguished with above-described embodiment, negative electrode tab preparation includes negative electrode slurry preparation, negative electrode tab compacting, and wherein cathode is starched
Material preparation is uniformly mixed to get negative electrode slurry by negative electrode material and solvent, and negative electrode tab, which is compressed to the coated equipment of negative electrode slurry, to be made to apply
Layer be coated uniformly on the two sides of collector, the negative electrode material that slurry is formed on a current collector with a thickness of 90 μm of (negative electrode materials
It includes but not limited to following any for can also being in unilateral thickness: 91,92,93,94,95,96,97,98,99,100,101,
102、103、104、105、106、107、108、109、110、111、112、113、114、115、116、117、118、119、120、
121、122、123、124、125、126、127、128、129、130、131、132、133、134、135、136、137、138、139、
140, other arbitrary values in 141,142,143,144,145,146,147,148,149,150 μm and 90-150 μ m),
And with 1.2g/cm3The density of size rolls that (it includes but not limited to following any for rolling density and can also being: 1.3g/cm3、1.4g/
cm3、1.5g/cm3、1.6g/cm3、1.7g/cm3、1.8g/cm3And 1.2-1.8g/cm3Other arbitrary values in range), punching
Cathode pole piece is made.
With above-mentioned all (including but not limited to the scheme of the invention including battery capacitor embodiment and preparation implementation, similarly hereinafter)
What embodiment distinguished, collector is corrosive aluminum foil.It is only (phase when being distinguished shown in this prescription case with aforementioned embodiment difference
Same parameter situation is excluded), battery capacitor sample tests it and carries out constant current charge and discharge test, battery under 2C current density
The specific energy of capacitor is greater than 87Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 85%.
It is distinguished with above-described embodiment, the corrosive aluminum foil surface as collector is also formed with aluminium amalgam.With aforementioned tool
When the difference of body embodiment is only difference shown in this prescription case (identical parameter situation is excluded), battery capacitor sample, test
It carries out constant current charge and discharge test under 2C current density, and the specific energy of battery capacitor is greater than 89Wh/Kg, recycles by 20000 times
Afterwards, capacity retention ratio is not less than 89%.
It is distinguished with above-described embodiment, the aluminium amalgam on corrosive aluminum foil surface is orientated on the surface.With aforementioned specific implementation
When example difference is only difference shown in this prescription case (identical parameter situation is excluded), battery capacitor sample tests it in 2C
Constant current charge and discharge test is carried out under current density, the specific energy of battery capacitor is greater than 90Wh/Kg, after 20000 circulations, capacity
Conservation rate is not less than 89%.
It is distinguished with above-described embodiment, the length of the protrusion part of the aluminium amalgam on corrosive aluminum foil surface is 0.01mm (rotten
The length for losing the protrusion part of the aluminium amalgam of aluminium foil surface can also be include but not limited to any in being exemplified below: 0.02,
0.03,0.014,0.016,0.017,0.019,0.022,0.023,0.025,0.027,0.028,0.029 and 0.01-
Other arbitrary values within the scope of 0.03mm).It is only (identical ginseng when being distinguished shown in this prescription case with aforementioned embodiment difference
Number situation is excluded), battery capacitor sample tests it and carries out constant current charge and discharge test under 2C current density, battery capacitor
Specific energy is greater than 91Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 90%.
It is distinguished with above-described embodiment, the differently- oriented directivity of aluminium amalgam is perpendicular to corrosive aluminum foil.With aforementioned specific implementation
When example difference is only difference shown in this prescription case (identical parameter situation is excluded), battery capacitor sample tests it in 2C
Constant current charge and discharge test is carried out under current density, the specific energy of battery capacitor is greater than 93Wh/Kg, after 20000 circulations, capacity
Conservation rate is not less than 90%.
It is distinguished with above-described embodiment, the differently- oriented directivity of aluminium amalgam is to tilt with corrosive aluminum foil surface.With it is aforementioned specific
When embodiment difference is only difference shown in this prescription case (identical parameter situation is excluded), battery capacitor sample tests it
Constant current charge and discharge test is carried out under 2C current density, the specific energy of battery capacitor is greater than 94Wh/Kg, after 20000 circulations,
Capacity retention ratio is not less than 91%.
It is distinguished with above-described embodiment, the differently- oriented directivity of aluminium amalgam is to tilt with corrosive aluminum foil surface, tilt angle
For 30 degree (tilt angle can also be include but not limited to be exemplified below in any: 31,32,33,34,35,36,37,38,
39, other arbitrary values within the scope of 40,41,42,43,44,45 and 130-45 degree).The interior aluminium mercury of the range of tilt angles
The binding performance between the layer structure of electrode slice is made to obtain the effect of enhancing 30-50% compared with when other directions are orientated together,
This be utilized pinning and inclination angle it is chimeric between cooperation obtain.It is only shown in this prescription case with aforementioned embodiment difference
(identical parameter situation is excluded), battery capacitor sample when difference, test it and carry out constant current charge and discharge under 2C current density
The specific energy of test, battery capacitor is greater than 96Wh/Kg, and after 20000 circulations, capacity retention ratio is not less than 93%.
This place embodiment is not exhaustive claimed midpoint of technical range and in embodiment technology
In scheme to single or multiple technical characteristics it is same replacement be formed by new technical solution, equally all the present invention claims
In the range of protection；Simultaneously the present invention program it is all enumerate or unlisted embodiment in, in the same embodiment each
Parameter is merely representative of an example (i.e. a kind of feasible scheme) for its technical solution, and between parameters and is not present stringent
Cooperation and qualified relation, wherein each parameter can be replaced mutually when stating and asking without prejudice to axiom and the present invention, special declaration
Except.
The technical means disclosed in the embodiments of the present invention is not limited to the technical means disclosed in the above technical means, and further includes
Technical solution consisting of any combination of the above technical features.The foregoing is a specific embodiment of the present invention, should refer to
Out, for those skilled in the art, without departing from the principle of the present invention, can also make several
Improvements and modifications, these modifications and embellishments are also considered to be within the scope of the present invention.
Claims (5)
1. a kind of big multiplying power hybrid battery capacitor, including the electrolyte and battery core in shell and shell, in which:
The battery core is assembled by positive plate, diaphragm and negative electrode tab overlapping；
The positive plate includes collector and the positive electrode for being formed in collection liquid surface, and the positive electrode includes
LiNi0.8Co 0.15Al0.05O2、LiFePO4, active carbon composite material；The positive electrode includes following mass percent: living
Property charcoal: 4-6%, binder 5-8%, conductive agent 3-8%, LiNi0.8Co 0.15Al0.05O2-LiFePO4Material: surplus；LiNi0.8Co0.15Al0.05O2-LiFePO4The composition of material are as follows: LiNi0.8Co 0.15Al0.05O2And LiFePO4Mass ratio be (0.1 ~ 9): 1；
The negative electrode tab includes collector and the negative electrode material for being formed in collection liquid surface, the negative electrode material include graphite,
The composite material of carbon nanotube, active carbon；The negative electrode material includes following mass percent: active carbon: 3-8%, binder 5-
8%, conductive agent 3-8%, graphite-carbon nano-tube material: surplus；Graphite-carbon nano-tube material composition are as follows: graphite and carbon nanotube
Mass ratio be 1:(0.001 ~ 0.15).
2. big multiplying power hybrid battery capacitor according to claim 1, which is characterized in that the conductive agent be conductive carbon black,
It is graphene, carbon nanotube, one or more of in Ketjen black.
3. big multiplying power hybrid battery capacitor according to claim 1, which is characterized in that the binder is polyvinylidene fluoride
It is alkene, polytetrafluoroethylene (PTFE), one or more of in butadiene-styrene rubber.
4. a kind of preparation method of big multiplying power hybrid battery capacitor as described in claim 1, including positive plate preparation, negative electrode tab
Preparation, wherein positive plate preparation include anode sizing agent preparation, positive plate compacting, wherein anode sizing agent preparation by positive electrode with it is molten
Agent is uniformly mixed to get anode sizing agent, and positive plate, which is compressed to the coated equipment of anode sizing agent, uniformly makes coating be coated in collector
On two sides, the unilateral side of positive electrode that slurry is formed on a current collector is with a thickness of 90-150 μm, and with 1.5-2.0g/cm3Size
Density roll, be punched positive plate is made.
5. the preparation method of big multiplying power hybrid battery capacitor according to claim 4, which is characterized in that the negative electrode tab system
Standby includes negative electrode slurry preparation, negative electrode tab compacting, and wherein negative electrode slurry preparation is uniformly mixed to get by negative electrode material with solvent negative
Pole slurry, negative electrode tab, which is compressed to the coated equipment of negative electrode slurry, is coated in coating uniform on the two sides of collector, and slurry is collecting
The negative electrode material formed on fluid with a thickness of 90-150 μm, and with 1.2-1.8g/cm3The density of size rolls, is punched and is made
Negative electrode tab.
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| CN105336504B (en) * | 2015-09-24 | 2017-05-10 | 宁波中车新能源科技有限公司 | Hybrid capacitor battery |
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