CN109244360A - Binder and its application, anode sizing agent and its application, anode slice of lithium ion battery, lithium ion battery and its application - Google Patents
Binder and its application, anode sizing agent and its application, anode slice of lithium ion battery, lithium ion battery and its application Download PDFInfo
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- CN109244360A CN109244360A CN201811193546.8A CN201811193546A CN109244360A CN 109244360 A CN109244360 A CN 109244360A CN 201811193546 A CN201811193546 A CN 201811193546A CN 109244360 A CN109244360 A CN 109244360A
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- binder
- anode
- sizing agent
- ion battery
- lithium ion
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of binder and its application, anode sizing agent and its application, anode slice of lithium ion battery, lithium ion battery and its applications, belong to anode sizing agent technical field.The present invention provides a kind of binders, including Kynoar and modified polyvinilidene fluoride；Wherein, the modified polyvinilidene fluoride is the modified polyvinilidene fluoride containing carbonyl；The weight ratio of the Kynoar and modified polyvinilidene fluoride is 4.8-5.2:1.The electrostatic interaction between carbonyl and collector in modified polyvinilidene fluoride considerably increases the cohesive force in anode sizing agent between active material and collector, by the proportion for adjusting Kynoar and modified polyvinilidene fluoride in binder, make the binder both and ensure that the bonding between the active material in anode sizing agent, between active material and collector, also reduce usage amount of the binder in anode sizing agent, so that the compacted density of anode pole piece can be improved when the binder is used as positive electrode coating.
Description
Technical field
The invention belongs to anode sizing agent technical fields, and in particular to a kind of binder and its application, anode sizing agent and its answer
With, anode slice of lithium ion battery, lithium ion battery and its application.
Background technique
Lithium ion battery has many advantages, such as that specific energy is high, has extended cycle life and pollution-free, can large-scale application in new energy
The fields such as source electric vehicle, smart phone, digital camera, laptop.Power battery and system are improved recently as country
Energy density threshold requirement further encourages high-performance power battery application, clearly proposes lithium-ion-power cell from now on
Developing goal, it is desirable that arrive the year two thousand twenty, lithium-ion-power cell monomer weight energy density reaches 300Wh/kg, to lithium ion battery
Energy density propose specific index request.
Lithium ion battery in the production process, material compacted density be counted as battery material energy density reference index it
One, there is large effect to battery performance.In general, compacted density is bigger, and the capacity of battery is also higher, the energy of battery
Density is also higher.Compacted density=surface density/(thickness-afflux body thickness after pole piece roll-in).Usual lithium ion cell electrode
The surface density and binder of piece and the dosage of conductive agent can all influence the compacted density of pole piece, the addition of conductive agent and binder
It is lower to measure more more then pole piece compaction densities.
In the method for increasing battery energy density, the surface density for increasing material is a kind of more commonly used method, but this
But there are many defects in kind method, for example, this method is easy to cause pole piece that over-voltage occurs, and pole piece over-voltage will cause battery to hold
The problems such as amount reduces, and circulation deteriorates, and internal resistance increases.By taking positive cobalt nickel lithium manganate ternary material as an example, pole piece over-voltage can make spherical shape
Ternary material large area is broken, and there are much little particles departing from secondary ball on newly generated surface, these little particles can be because
It is fallen from pole piece to be not exposed to binder Kynoar (PVDF), as being not exposed to conductive agent and making
Pole piece electric conductivity local deteriorated.The generation on new surface is but also the specific surface area of material increases, the contact surface increasing with electrolyte
Greatly, side reaction increases, so that battery performance be caused to decline.Positive over-voltage also will cause aluminium foil deformation, and pole piece, which becomes fragile, to be easily snapped off,
The internal resistance of cell increases.
In addition, the extruding degree between material granule is excessive in the pole piece of over-voltage, cause pole piece porosity low, pole piece is inhaled
The amount for receiving electrolyte can also reduce, and electrolyte is difficult to penetrate into inside pole piece, and direct consequence is exactly that material electrolyte protects liquid energy
Power is deteriorated, and the specific capacity of material, which plays, to be deteriorated, and cycle performance deteriorates.
It is therefore desired to provide a kind of method that can be improved electrodes of lithium-ion batteries compacted density, it is able to solve
At least one of above problem.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
One of the objects of the present invention is to provide a kind of binder, which can be effectively reduced making for positive electrode binder
Dosage is able to solve at least one of above problem to improve the compacted density of anode pole piece.
The second object of the present invention is to provide application of the above-mentioned binder in anode sizing agent；It include above-mentioned binder
Anode sizing agent can guarantee the bonding between the active material in anode sizing agent while reducing consumption of binder, and it is living
Bonding between property substance and collector.
The third object of the present invention is to provide a kind of anode sizing agent；The anode sizing agent situation less in consumption of binder
Under, it can make between the active material in anode sizing agent, active material and collector effectively bond.
The fourth object of the present invention is that providing above-mentioned anode sizing agent is preparing the application in anode slice of lithium ion battery；
Consumption of binder is less in above-mentioned anode sizing agent, is coated in the obtained positive film in surface of anode slice of lithium ion battery with it
The dosage of binder is less.
The fifth object of the present invention is to provide a kind of anode slice of lithium ion battery；The anode slice of lithium ion battery institute
It is less with the consumption of binder in anode sizing agent, be conducive to the compacted density for improving anode slice of lithium ion battery.
The sixth object of the present invention is to provide a kind of lithium ion battery；The collection liquid surface of the lithium ion battery is coated with
Above-mentioned slurry, material compacted density are higher.
The seventh object of the present invention is to provide above-mentioned lithium ion battery in smart phone, digital camera, laptop
Or the application in electric vehicle；The material compacted density of the lithium ion battery is higher, can satisfy smart phone, digital camera, pen
Remember the requirement of this computer or electric vehicle to energy density.
In a first aspect, providing a kind of binder, including Kynoar and modified polyvinilidene fluoride；
Wherein, the modified polyvinilidene fluoride is the modified polyvinilidene fluoride containing carbonyl；
The weight ratio of the Kynoar and modified polyvinilidene fluoride is 4.8-5.2:1.
Preferably, the weight average molecular weight of the Kynoar is 600,000-70 ten thousand；
Preferably, the weight average molecular weight of the modified polyvinilidene fluoride is 1,000,000-120 ten thousand；
Preferably, the modified polyvinilidene fluoride is Solef 5130；
Preferably, the weight ratio of the Kynoar and modified polyvinilidene fluoride is 5:1.
Second aspect provides application of the above-mentioned binder in anode sizing agent.
The third aspect provides a kind of anode sizing agent, including the binder, positive active material and conductive agent.
Preferably, the weight ratio of the binder, positive active material and conductive agent is 0.8-1.5:97-98.2:1-
1.5；
Preferably, the positive active material is nickel cobalt lithium aluminate ternary material and/or cobalt nickel lithium manganate ternary material；
Preferably, the conductive agent is the combination of carbon nanotube and conductive black, the weight of carbon nanotube and conductive black
Than for 0.9-1.1:0.9-1, preferably 1:1；
Preferably, the component of the anode sizing agent further includes solvent；
Preferably, the weight ratio of the solvent and positive active material is 30-35:100；
Preferably, the solvent is N-Methyl pyrrolidone.
Fourth aspect provides above-mentioned anode sizing agent and is preparing the application in anode slice of lithium ion battery.
5th aspect, provides a kind of anode slice of lithium ion battery, including plus plate current-collecting body, the plus plate current-collecting body
Front and/or the back side are coated with positive film, and the anode film is solidified by the anode sizing agent.
Preferably, the plus plate current-collecting body is aluminium foil, preferably 12 μm -20 μm of aluminium foil；
Preferably, the front and back of the plus plate current-collecting body is coated with positive film；
Preferably, the surface density of the positive film is 45mg/cm2-52mg/cm2。
6th aspect, provides a kind of lithium ion battery, including above-mentioned anode slice of lithium ion battery.
7th aspect, provides above-mentioned lithium ion battery in smart phone, digital camera, laptop or electric vehicle
Application.
The present invention provides a kind of binder, which includes Kynoar and modified polyvinilidene fluoride, is modified poly-
Vinylidene is grafted on the strand of Kynoar introduces carbonyl functional group, thus when the anode slurry for including the binder
When material is coated in collection liquid surface, the electrostatic interaction between carbonyl and collector considerably increase in anode sizing agent active material and
Cohesive force between collector makes polyvinylidene fluoride by adjusting the proportion of Kynoar and modified polyvinilidene fluoride in binder
The weight ratio of alkene and modified polyvinilidene fluoride be 4.8-5.2:1, the binder both enhanced the active material in anode sizing agent it
Between bonding, also enhance the bonding between active material and collector, while also reducing binder in anode sizing agent
Usage amount, so that the compacted density of anode pole piece can be improved when the binder is used as positive electrode coating.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the structural schematic diagram for the anode pole piece that the present invention is coated with positive electrode coating.
Icon: 1- plus plate current-collecting body aluminium foil；2- anode film.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with examples and drawings, but those skilled in the art
Member will be understood that the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not infused in embodiment
Bright actual conditions person, carries out according to conventional conditions or manufacturer's recommended conditions.Production firm is not specified in agents useful for same or instrument
Person is the conventional products that can be obtained by commercially available purchase.
In a first aspect, providing a kind of binder, including Kynoar and modified polyvinilidene fluoride；
Wherein, modified polyvinilidene fluoride is the modified polyvinilidene fluoride containing carbonyl；
The weight ratio of Kynoar and modified polyvinilidene fluoride is 4.8-5.2:1.
The binder includes Kynoar and modified polyvinilidene fluoride, point of the modified polyvinilidene fluoride in Kynoar
Grafting introduces carbonyl functional group in subchain, thus when the anode sizing agent for including the binder is coated in collection liquid surface, carbonyl
Electrostatic interaction between base and collector considerably increases the cohesive force in anode sizing agent between active material and collector.
By adjusting the proportion of Kynoar and modified polyvinilidene fluoride in binder, making Kynoar and being modified poly-
The weight ratio of vinylidene is 4.8-5.2:1, which had both enhanced the bonding between the active material in anode sizing agent,
The bonding between active material and collector is enhanced, while also reducing usage amount of the binder in anode sizing agent, thus
When so that the binder being used as positive electrode coating, the compacted density of anode pole piece can be improved.It is typical but non-limiting, polyvinylidene fluoride
The weight ratio of alkene and modified polyvinilidene fluoride is 4.8:1,4.9:1,5.0:1,5.1:1 or 5.2:1.
As further preferred technical solution, the weight average molecular weight of Kynoar is 600,000-70 ten thousand, Kynoar
Typical but non-limiting weight average molecular weight be 600,000,60.5 ten thousand, 610,000,61.5 ten thousand, 620,000,62.5 ten thousand, 630,000,63.5 ten thousand,
640000,64.5 ten thousand, 650,000,65.5 ten thousand, 660,000,66.5 ten thousand, 670,000,67.5 ten thousand, 680,000,68.5 ten thousand, 690,000,69.5 ten thousand or 70
Ten thousand.It include that weight average molecular weight is by reasonably adjusting the weight average molecular weight of Kynoar in the preferred embodiment
600000-70 ten thousand Kynoar can guarantee to glue between the active material in anode sizing agent, between active material and collector
While knot, further decrease usage amount of the binder in anode sizing agent, thus further improve be coated with include this
The compacted density of the pole piece of the positive electrode coating of binder.Weight average molecular weight is poor less than the caking property of 600,000 Kynoar,
It just needs for enhancing caking property using larger amount of Kynoar, and the usage amount of Kynoar is bigger, it will be so that pole piece
Compacted density it is lower.
As further preferred technical solution, the weight average molecular weight of modified polyvinilidene fluoride is 1,000,000-120 ten thousand, modified
The typical but non-limiting weight average molecular weight of Kynoar is 1,000,000,1,010,000,1,020,000,1,030,000,1,040,000,1,050,000,106
Ten thousand, 1,070,000,1,080,000,1,090,000,1,100,000,1,110,000,1,120,000,1,130,000,1,140,000,1,150,000,1,160,000,1,170,000,1,180,000,
1190000 or 1,200,000.In the preferred embodiment, by reasonably adjusting the weight average molecular weight of modified polyvinilidene fluoride, include
Having weight average molecular weight is that 1,000,000-120 ten thousand modified polyvinilidene fluoride can guarantee between active material in anode sizing agent, is living
While bonding between property substance and collector, usage amount of the binder in anode sizing agent is further decreased, is further increased
The compacted density of pole piece coated with the positive electrode coating for including the binder.Modification of the weight average molecular weight greater than 1,200,000 is poly-
Vinylidene will need additional condition such as to increase mixing time, and can just be completely dissolved in a solvent compared with indissoluble solution.
As further preferred technical solution, modified polyvinilidene fluoride is Solef 5130；In the preferred embodiment party
In formula, the Solef 5130 of specific dosage is matched with Kynoar, can effectively enhance the active material in anode sizing agent
Between, bond between active material and collector.
As further preferred technical solution, the weight ratio of Kynoar and modified polyvinilidene fluoride is 5:1；At this
In preferred embodiment, by reasonably adjusting the proportion of Kynoar and modified polyvinilidene fluoride, it can further increase
It is bonded between active material in anode sizing agent, between active material and collector, reduces the usage amount of binder.
Second aspect provides application of the above-mentioned binder in anode sizing agent.
It include that the anode sizing agent of above-mentioned binder can guarantee in anode sizing agent while reducing consumption of binder
The bonding between bonding and active material and collector between active material.
The third aspect provides a kind of anode sizing agent, including binder, positive active material and conductive agent.
The anode sizing agent includes above-mentioned binder, positive active material and conductive agent, in the less situation of consumption of binder
Under, it can make between the active material in anode sizing agent, active material and collector effectively bond.
As further preferred technical solution, the weight ratio of binder, positive active material and conductive agent is 0.8-
1.5:97-98.2:1-1.5, by weight, the typical but non-limiting parts by weight of binder are 0.8 part, 0.9 part, 1 part, 1.1
Part, 1.2 parts, 1.3 parts, 1.4 parts or 1.5 parts, the typical but non-limiting parts by weight of positive active material be 97 parts, 97.1 parts,
97.2 parts, 97.3 parts, 97.4 parts, 97.5 parts, 97.6 parts, 97.7 parts, 97.8 parts, 97.9 parts, 98 parts, 98.1 parts or 98.2 parts,
The typical but non-limiting parts by weight of conductive agent are 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts or 1.5 parts.In the preferred reality
It applies in mode, weight ratio is the anode that binder, positive active material and the conductive agent of 0.8-1.5:97-98.2:1-1.5 obtains
Slurry still enables to bond between positive active material while the dosage of binder is less, so that positive electrode active material
Matter and collector bonding.Conductive agent content can suitably obtain higher discharge capacity and preferable cycle performance；Content too it is low then
Electronic conduction channel is few, is unfavorable for high current charge-discharge；Content is too high, reduces the relative amount of active material, holds battery
Amount reduces.
As further preferred technical solution, positive active material is nickel cobalt lithium aluminate ternary material and/or nickel cobalt manganese
Sour lithium ternary material.
As further preferred technical solution, conductive agent is the combination of carbon nanotube and conductive black, carbon nanotube and
The weight ratio of conductive black is 0.9-1.1:0.9-1, and by weight, the typical but non-limiting parts by weight of carbon nanotube are 0.9
Part, 0.91 part, 0.94 part, 0.95 part, 0.96 part, 0.97 part, 0.98 part, 0.99 part, 1 part, 1.02 parts, 1.04 parts, 1.05 parts,
1.06 parts, 1.08 parts, 1.09 parts or 1.1 parts, the typical but non-limiting parts by weight of conductive black are 0.9 part, 0.91 part, 0.94
Part, 0.95 part, 0.96 part, 0.97 part, 0.98 part, 0.99 part or 1 part；In the preferred embodiment, specific dosage (weight
Than for 0.9-1.1:0.9-1) carbon nanotube and conductive black can further increase the ratio of positive active material, be conducive to
Increase the capacity of battery.
As further preferred technical solution, conductive agent is the combination of carbon nanotube and conductive black, carbon nanotube and
The weight ratio of conductive black is 1:1.
As further preferred technical solution, the component of anode sizing agent further includes solvent.
As further preferred technical solution, the weight ratio of solvent and positive active material is 30-35:100, solvent with
The typical but non-limiting weight ratio of positive active material be 30:100,30.5:100,31:100,31.5:100,32:100,
32.5:100,33:100,33.5:100,34:100,34.5:100 or 35:100.
As further preferred technical solution, solvent is N-Methyl pyrrolidone；N-Methyl pyrrolidone enables to
Binder, positive active material, conductive agent and N-Methyl pyrrolidone are sufficiently mixed, and final anode sizing agent is had and is closed
Suitable viscosity can be coated on pole piece.
Fourth aspect provides above-mentioned anode sizing agent and is preparing the application in anode slice of lithium ion battery.
Consumption of binder is less in above-mentioned anode sizing agent, with the surface of anode sizing agent coating anode slice of lithium ion battery
The dosage of binder is less in obtained positive film, is conducive to the compacted density for improving anode slice of lithium ion battery.
5th aspect, provides a kind of anode slice of lithium ion battery, including plus plate current-collecting body, the front of plus plate current-collecting body
And/or the back side is coated with positive film, positive film is solidified by anode sizing agent.
Consumption of binder in anode sizing agent used in the anode slice of lithium ion battery is less, is conducive to improve lithium-ion electric
The compacted density of pond anode pole piece.
It is understood that " solidification " herein refers to that anode sizing agent loses liquid portion, solid-state is become from liquid, herein
Refer to that anode sizing agent loses solvent, solid positive film is changed by the anode sizing agent of liquid.
As further preferred technical solution, plus plate current-collecting body is aluminium foil, preferably 12 μm -20 μm of aluminium foil, aluminium foil
It is typical but non-limiting with a thickness of 12 μm, 12.5 μm, 13 μm, 13.5 μm, 14 μm, 14.5 μm, 15 μm, 15.5 μm, 16 μm,
16.5 μm, 17 μm, 17.5 μm, 18 μm, 18.5 μm, 19 μm, 19.5 μm or 20 μm.
As further preferred technical solution, the front and back of plus plate current-collecting body is coated with positive film；It is excellent at this
In the embodiment of choosing, anode sizing agent is coated simultaneously by the front and back in plus plate current-collecting body, so that plus plate current-collecting body
Front and back is all coated with positive film, so that battery capacity is high.
As further preferred technical solution, the surface density of positive film is 45mg/cm2-52mg/cm2, positive film
Typical but non-limiting surface density is 45mg/cm2、45.5mg/cm2、46mg/cm2、46.5mg/cm2、47mg/cm2、
47.5mg/cm2、48mg/cm2、48.5mg/cm2、49mg/cm2、49.5mg/cm2、50mg/cm2、50.5mg/cm2、51mg/cm2、
51.5mg/cm2Or 52mg/cm2.In the preferred embodiment, by reasonably adjusting the surface density of positive film, surface density
For 45mg/cm2-52mg/cm2Positive film enable to anode capacity height and battery energy density higher.
6th aspect, provides a kind of lithium ion battery, including above-mentioned anode slice of lithium ion battery.
The collection liquid surface of the lithium ion battery is coated with above-mentioned slurry, and material compacted density is higher, is conducive to improve just
Pole capacity and battery energy density.
7th aspect, provides above-mentioned lithium ion battery in smart phone, digital camera, laptop or electric vehicle
Application.
The material compacted density of the lithium ion battery is higher, can satisfy smart phone, digital camera, laptop or
Requirement of the electric vehicle to energy density.
Technical solution of the present invention is described further below in conjunction with embodiment and comparative example.
Embodiment 1
1, binder
A kind of binder, including Kynoar (PVDF) and modified polyvinilidene fluoride.
Wherein, Kynoar is Solef 6020, and the molecular weight of Kynoar is 700,000；Modified polyvinilidene fluoride is
Solef 5130, the molecular weight of modified polyvinilidene fluoride are 1,100,000；The weight ratio of Kynoar and modified polyvinilidene fluoride is
5:1。
2, anode sizing agent
A kind of anode sizing agent, including binder, nickel cobalt lithium aluminate, conductive agent and N-Methyl pyrrolidone, conductive agent are attached most importance to
Measure the carbon nanotube and conductive black than 1:1.
The weight ratio of binder, nickel cobalt lithium aluminate and conductive agent is 1.2:97.3:1.5, N-Methyl pyrrolidone and nickel cobalt
The weight ratio of lithium aluminate is 32.5:100.
The preparation of anode sizing agent is the tool by mixing binder, nickel cobalt lithium aluminate, conductive agent and N-Methyl pyrrolidone
Body is as follows:
1) the binder 12.3g for, taking the composition for the PVDF and modified PVDF that weight ratio is 5:1, is dissolved in the N- first of 164g
In base pyrrolidones (NMP), glue, solid content 7% are obtained.
2) 7.7g conductive black Super P and 7.7g carbon nano tube paste, is added into above-mentioned 1) glue to stir evenly.
3) nickel cobalt lithium aluminate 500g, is added into above-mentioned 2) slurry, stirring makes binder, conductive agent and positive electrode active material
Matter sufficiently infiltrates.
4) nickel cobalt lithium aluminate 500g, is added into above-mentioned 3) slurry, stirs evenly, after adjusting viscosity with the NMP of 161g, takes out
Vacuum obtains anode sizing agent.
3, anode slice of lithium ion battery
As shown in Figure 1, a kind of anode slice of lithium ion battery, includes plus plate current-collecting body aluminium foil (1), plus plate current-collecting body aluminium foil
(1) front and back is coated with positive film (2), and positive film (2) is solidified by anode sizing agent.
Anode slice of lithium ion battery the preparation method is as follows:
1), anode sizing agent is coated on 12 μm of aluminium foils, coating surface density is 50mg/cm2, drying.
2) roll-in, is carried out to preset thickness to anode pole piece with roll squeezer.
Anode pole piece after roll-in is subjected to 180 ° of doublings along straight line, then in 180 ° of folding line opposite direction doubling, continuous 3 times
Doubling operation is stated, whether observation pole piece occurs being broken or whether have loophole.If do not occurred being broken or loophole, then continue to drop
Low pole piece thickness increases compacted density, until pole piece occurs being broken or loophole, record pole piece does not occur finally being broken or light transmission
The compacted density in hole, the results are shown in Table 5.
Embodiment 2
1, binder
A kind of binder, including Kynoar (PVDF) and modified polyvinilidene fluoride.
Wherein, Kynoar is Solef 6020, and the molecular weight of Kynoar is 700,000；Modified polyvinilidene fluoride is
Solef 5130, the molecular weight of modified polyvinilidene fluoride are 1,100,000；The weight ratio of Kynoar and modified polyvinilidene fluoride is
5:1。
2, anode sizing agent
A kind of anode sizing agent, including binder, nickle cobalt lithium manganate, conductive agent and N-Methyl pyrrolidone, conductive agent are attached most importance to
Measure the carbon nanotube and conductive black than 1:1.
The weight ratio of binder, nickle cobalt lithium manganate and conductive agent is 1.3:97.2:1.5, N-Methyl pyrrolidone and nickel cobalt
The weight ratio of LiMn2O4 is 32.5:100.
The preparation of anode sizing agent is the tool by mixing binder, nickle cobalt lithium manganate, conductive agent and N-Methyl pyrrolidone
Body is as follows:
1) the binder 13.4g for, taking the composition for the PVDF and modified PVDF that weight ratio is 5:1, is dissolved in the N- first of 178g
In base pyrrolidones (NMP), glue, solid content 7% are obtained.
2) 7.7g conductive black Super P and 7.7g carbon nano tube paste, is added into above-mentioned 1) glue to stir evenly.
3) nickle cobalt lithium manganate 500g, is added into above-mentioned 2) slurry, stirring makes binder, conductive agent and positive electrode active material
Matter sufficiently infiltrates.
4) nickle cobalt lithium manganate 500g, is added into above-mentioned 3) slurry, stirs evenly, after adjusting viscosity with the NMP of 147.5g,
It vacuumizes, obtains anode sizing agent.
3, anode slice of lithium ion battery
As shown in Figure 1, a kind of anode slice of lithium ion battery, includes plus plate current-collecting body aluminium foil (1), plus plate current-collecting body aluminium foil
(1) front and back is coated with positive film (2), and positive film (2) is solidified by anode sizing agent.
Anode slice of lithium ion battery the preparation method is as follows:
1), anode sizing agent is coated on 12 μm of aluminium foils, coating surface density is 50mg/cm2, drying.
2) roll-in, is carried out to preset thickness to anode pole piece with roll squeezer.
Anode pole piece after roll-in is subjected to 180 ° of doublings along straight line, then in 180 ° of folding line opposite direction doubling, continuous 3 times
Doubling operation is stated, whether observation pole piece occurs being broken or whether have loophole.If do not occurred being broken or loophole, then continue to drop
Low pole piece thickness increases compacted density, until pole piece occurs being broken or loophole, record pole piece does not occur finally being broken or light transmission
The compacted density in hole, the results are shown in Table 5.
Embodiment 3
1, binder
A kind of binder, including Kynoar (PVDF) and modified polyvinilidene fluoride.
Wherein, Kynoar is Solef 6020, and the molecular weight of Kynoar is 650,000；Modified polyvinilidene fluoride is
Solef 5130, the molecular weight of modified polyvinilidene fluoride are 1,100,000；The weight ratio of Kynoar and modified polyvinilidene fluoride is
5:1。
2, anode sizing agent
A kind of anode sizing agent, including binder, nickel cobalt lithium aluminate, conductive agent and N-Methyl pyrrolidone, conductive agent are attached most importance to
Measure the carbon nanotube and conductive black than 1:1.
The weight ratio of binder, nickel cobalt lithium aluminate and conductive agent is 1.2:97.6:1.2, N-Methyl pyrrolidone and nickel cobalt
The weight ratio of lithium aluminate is 32.5:100.
The preparation of anode sizing agent is the tool by mixing binder, nickel cobalt lithium aluminate, conductive agent and N-Methyl pyrrolidone
Body is as follows:
1) the binder 12.3g for, taking the composition for the PVDF and modified PVDF that weight ratio is 5:1, is dissolved in the N- first of 164g
In base pyrrolidones (NMP), glue, solid content 7% are obtained.
2) 6.15g conductive black Super P and 6.15g carbon nano tube paste, is added into above-mentioned 1) glue to stir evenly.
3) nickel cobalt lithium aluminate 500g, is added into above-mentioned 2) slurry, stirring makes binder, conductive agent and positive electrode active material
Matter sufficiently infiltrates.
4) nickel cobalt lithium aluminate 500g, is added into above-mentioned 3) slurry, stirs evenly, after adjusting viscosity with the NMP of 161g, takes out
Vacuum obtains anode sizing agent.
3, anode slice of lithium ion battery
As shown in Figure 1, a kind of anode slice of lithium ion battery, includes plus plate current-collecting body aluminium foil (1), plus plate current-collecting body aluminium foil
(1) front and back is coated with positive film (2), and positive film (2) is solidified by anode sizing agent.
Anode slice of lithium ion battery the preparation method is as follows:
1), anode sizing agent is coated on 16 μm of aluminium foils, coating surface density is 48.5mg/cm2, drying.
2) roll-in, is carried out to preset thickness to anode pole piece with roll squeezer.
Anode pole piece after roll-in is subjected to 180 ° of doublings along straight line, then in 180 ° of folding line opposite direction doubling, continuous 3 times
Doubling operation is stated, whether observation pole piece occurs being broken or whether have loophole.If do not occurred being broken or loophole, then continue to drop
Low pole piece thickness increases compacted density, until pole piece occurs being broken or loophole, record pole piece does not occur finally being broken or light transmission
The compacted density in hole, the results are shown in Table 5.
Embodiment 4-5
Embodiment 4-5 and embodiment 3 the difference is that, Kynoar and modified polyvinilidene fluoride in binder
Weight ratio is different, specific as shown in table 1.
The weight ratio of Kynoar and modified polyvinilidene fluoride in 1 embodiment 4-5 of table
| The weight ratio of Kynoar and modified polyvinilidene fluoride | |
| Embodiment 4 | 4.8:1 |
| Embodiment 5 | 5.2:1 |
Embodiment 6-11
Embodiment 6-11 and embodiment 3 the difference is that, Kynoar and modified polyvinilidene fluoride in binder
Difference, the weight average molecular weight of Kynoar and modified polyvinilidene fluoride is as shown in table 2 in binder.
The weight average molecular weight of Kynoar and modified polyvinilidene fluoride in 2 embodiment 6-11 of table
| Kynoar | Modified polyvinilidene fluoride | |
| Embodiment 6 | 600000 | 1200000 |
| Embodiment 7 | 700000 | 1000000 |
| Embodiment 8 | 500000 | — |
| Embodiment 9 | 800000 | — |
| Embodiment 10 | — | 1300000 |
| Embodiment 11 | — | 900000 |
In table 2, "-" indicates identical as in embodiment 3.
Embodiment 12
Embodiment 12-13 and embodiment 3 the difference is that, binder, positive active material and led in anode sizing agent
The dosage of electric agent, it is specific as shown in table 3.
The parts by weight of binder, positive active material and conductive agent in 3 anode sizing agent of table
| Binder | Positive active material | Conductive agent | |
| Embodiment 12 | 0.8 part | 98.2 parts | 1 part |
| Embodiment 13 | 1.5 part | 97 parts | 1.5 part |
Comparative example 1
Comparative example 1 difference from example 1 is that, binder only has Kynoar, do not contain modified polyvinilidene fluorine
Ethylene.
Comparative example 2
Comparative example 2 difference from example 1 is that, binder only has modified polyvinilidene fluoride, without containing gathering inclined fluorine
Ethylene.
Comparative example 3-4
Comparative example 3-4 and embodiment 3 the difference is that, Kynoar and modified polyvinilidene fluoride in binder
Weight ratio is different, specific as shown in table 4.
The weight ratio of Kynoar and modified polyvinilidene fluoride in 4 comparative example 3-4 of table
| The weight ratio of Kynoar and modified polyvinilidene fluoride | |
| Comparative example 3 | 4:1 |
| Comparative example 4 | 5.5:1 |
Test example 1
The anode pole piece after embodiment 1-13 and comparative example 1-4 roll-in is subjected to 180 ° of doublings along straight line respectively, then along folding
Whether 180 ° of trace opposite direction doubling, continuous 3 above-mentioned doubling operations, observation pole piece occur being broken or whether have loophole.Such as
Do not occur being broken or loophole, then continues to reduce pole piece thickness, increase compacted density, until pole piece occurs being broken or loophole,
Record pole piece embodiment 1-13 and comparative example 1-4 does not occur finally being broken or the compacted density of loophole, obtains embodiment 1-13
It is as shown in table 5 with the positive compacted density of comparative example 1-4.
The positive compacted density of table 5 embodiment 1-13 and comparative example 1-4
Test result shows the anode pole piece of 1-13 of embodiment of the present invention compacted density with higher, specifically, implements
The compacted density of example 1-13 anode pole piece is all in 3.5g/cm3More than, the compacting of embodiment 1-7 and embodiment 12-13 anode pole piece
Density has all reached 3.7g/cm3More than.
It should be understood that the content being not described in detail in the explanation of above-mentioned preparation method, is those skilled in the art
The Common Parameters being readily apparent that, therefore can be omitted detailed description thereof.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of binder, which is characterized in that including Kynoar and modified polyvinilidene fluoride；
Wherein, the modified polyvinilidene fluoride is the modified polyvinilidene fluoride containing carbonyl；
The weight ratio of the Kynoar and modified polyvinilidene fluoride is 4.8-5.2:1.
2. binder according to claim 1, which is characterized in that the weight average molecular weight of the Kynoar is 600,000-
700000；
Preferably, the weight average molecular weight of the modified polyvinilidene fluoride is 1,000,000-120 ten thousand；
Preferably, the modified polyvinilidene fluoride is Solef 5130；
Preferably, the weight ratio of the Kynoar and modified polyvinilidene fluoride is 5:1.
3. application of the binder of any of claims 1 or 2 in anode sizing agent.
4. a kind of anode sizing agent, which is characterized in that including binder of any of claims 1 or 2, positive active material and conduction
Agent.
5. anode sizing agent according to claim 4, which is characterized in that the weight of binder, positive active material and conductive agent
Amount is than being 0.8-1.5:97-98.2:1-1.5；
Preferably, the positive active material is nickel cobalt lithium aluminate ternary material and/or cobalt nickel lithium manganate ternary material；
Preferably, the conductive agent is the combination of carbon nanotube and conductive black, and the weight ratio of carbon nanotube and conductive black is
0.9-1.1:0.9-1, preferably 1:1；
Preferably, the component of the anode sizing agent further includes solvent；
Preferably, the weight ratio of the solvent and positive active material is 30-35:100；
Preferably, the solvent is N-Methyl pyrrolidone.
6. anode sizing agent described in claim 4 or 5 is preparing the application in anode slice of lithium ion battery.
7. a kind of anode slice of lithium ion battery, including plus plate current-collecting body, which is characterized in that the front of the plus plate current-collecting body
And/or the back side is coated with positive film, the anode film is solidified by anode sizing agent described in claim 4 or 5.
8. anode slice of lithium ion battery according to claim 7, which is characterized in that the plus plate current-collecting body is aluminium foil,
Preferably 12 μm -20 μm of aluminium foil；
Preferably, the front and back of the plus plate current-collecting body is coated with positive film；
Preferably, the surface density of the positive film is 45mg/cm2-52mg/cm2。
9. a kind of lithium ion battery, which is characterized in that including anode slice of lithium ion battery described in claim 7 or 8.
10. lithium ion battery as claimed in claim 9 answering in smart phone, digital camera, laptop or electric vehicle
With.
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| CN112151755A (en) * | 2020-09-08 | 2020-12-29 | 江苏塔菲尔新能源科技股份有限公司 | Positive plate and battery |
| CN115133035A (en) * | 2022-08-30 | 2022-09-30 | 宁德时代新能源科技股份有限公司 | Positive electrode slurry, method for producing same, secondary battery, battery module, battery pack, and electric device |
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| CN108336355A (en) * | 2017-01-17 | 2018-07-27 | 中航锂电（洛阳）有限公司 | A kind of lithium ion battery anode glue size and preparation method thereof |
| CN108370026A (en) * | 2015-12-10 | 2018-08-03 | 株式会社钟化 | Nonaqueous electrolytic solution secondary battery |
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| CN103429628A (en) * | 2011-01-06 | 2013-12-04 | 三菱丽阳株式会社 | Modifier for polyvinylidene fluoride, binder resin composition for batteries, secondary cell electrode, and battery |
| CN108370026A (en) * | 2015-12-10 | 2018-08-03 | 株式会社钟化 | Nonaqueous electrolytic solution secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112151755A (en) * | 2020-09-08 | 2020-12-29 | 江苏塔菲尔新能源科技股份有限公司 | Positive plate and battery |
| CN115133035A (en) * | 2022-08-30 | 2022-09-30 | 宁德时代新能源科技股份有限公司 | Positive electrode slurry, method for producing same, secondary battery, battery module, battery pack, and electric device |
| CN115133035B (en) * | 2022-08-30 | 2023-03-10 | 宁德时代新能源科技股份有限公司 | Positive electrode slurry, method for producing same, secondary battery, battery module, battery pack, and electric device |
| WO2024045505A1 (en) * | 2022-08-30 | 2024-03-07 | 宁德时代新能源科技股份有限公司 | Binder composition, positive electrode slurry, secondary battery, battery module, battery pack, and electric device |
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