CN107240721A - The preparation method of bipolar electrode and lithium ion battery and lithium ion battery - Google Patents
The preparation method of bipolar electrode and lithium ion battery and lithium ion battery Download PDFInfo
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- CN107240721A CN107240721A CN201710389586.9A CN201710389586A CN107240721A CN 107240721 A CN107240721 A CN 107240721A CN 201710389586 A CN201710389586 A CN 201710389586A CN 107240721 A CN107240721 A CN 107240721A
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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- H01M4/64—Carriers or collectors
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/029—Bipolar electrodes
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Abstract
The present invention relates to technical field of lithium ion, the preparation method for specifically disclosing a kind of bipolar electrode and lithium ion battery and lithium ion battery.The bipolar electrode includes collector, and the collector has just relative first surface and second surface；Also include outwards folding the first conductive layer set, positive-active layer successively from the first surface；And the second conductive layer set, negative electrode active layer are outwards folded successively from the second surface；Also include first conductive layer, collector, the second conductive layer carrying out firm fluid sealant, the fluid sealant is stacked at first conductive layer, collector, the surface of the second conductive layer, and the thickness on first conductive layer surface is identical with the thickness of positive-active layer, the thickness on second conductive layer surface is identical with the thickness of negative electrode active layer.The bipolar electrode that the present invention is provided can effectively improve the security and uniformity of lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of bipolar electrode and lithium ion battery and lithium from
The preparation method of sub- battery.
Background technology
Environmental pollution and oil shortage are the problems that various countries worldwide is all faced, and electric automobile can be used as alleviation
Even solve the scheme of the two problems --- the rigid demand of people's go off daily can be met and environment is not caused directly
The pollution connect.And one of key technology of Development of EV is exactly electrokinetic cell.
Have that energy density is high, operating voltage is high due to lithium ion battery, have extended cycle life, memory-less effect etc. it is a series of
Advantage, has become electrokinetic cell used for electric vehicle and receives much concern.To be applicable electric automobile, it is necessary to by multiple electrokinetic cells
Being together in series ensures output work hastily.But connect and very high is required to battery with two side terminals, according to current battery manufacture skill
Art, the battery consistency being together in series is difficult to ensure.Therefore, uniformity and security have become restriction Development of Electric Vehicles
Technical bottleneck.
A good solution think of can be provided for above mentioned problem by preparing bipolarity high-tension battery by internal superposition series connection
Road.Because bipolarity lithium ion battery is to form positive pole and negative pole respectively in the both sides of collector, barrier film is placed on neighboring bipolar
In the middle of electrode, the energy storage device of electrolyte, multiple stackings and layer is filled；This battery can realize that cell exports higher work
Make voltage.In addition, each position of the battery of this structure per a piece of pole plate, per a piece of pole plate, current density is all equal, and
And current density can also be very small, equal different with degree of aging of the active material extent of reaction will be not present in such inside battery
Weigh sex chromosome mosaicism, can effectively improve battery with two side terminals.
But the bipolar current collector defect of bipolar battery is than larger at present, as traditional bipolar current collector used is
Copper-Aluminum compound paper tinsel or aluminium nickel composite insulating foil, foil thickness are less than 100 μm, it is easy to produce hole.And once deposited in foil used
In micropore, electrolyte is easily entered, and causes battery to occur short circuit.When aluminium foil hole, be easily caused another side copper foil or
Oxide etch occurs for person's nickel foil.These problems can cause high voltage bipolar battery to there is potential safety hazard.
Application No. CN103219521A patent of invention discloses a kind of bipolar current collector and preparation method thereof, specifically
It is the increase one layer of polymeric barrier layer between aluminium foil and non-aluminum conductive layer, is coated with the polymer filled with conducting particles.This
Method needs repeatedly to be coated, complex process and it cannot be guaranteed that conducting particles is evenly distributed.
Application No. CN101076915A patent of invention discloses bipolar battery, but it has electrolyte and oozed out and causes
The problem of liquid connects short circuit, in order to solve the problem, uses polymer gel electrolyte in dielectric substrate.
Application No. CN104577132A patent of invention discloses a kind of bipolar current collector and preparation method thereof, specifically
Include for bipolar current collector above and below conducting base film, polymer barrier film layer and conductive shunting layer, conducting base film
Surface is covered with polymer barrier film layer and conductive shunting layer, and polymer barrier film layer is located at conducting base film and conductive point
Between fluid layer and staggeredly complementation is covered in the upper and lower surface of conducting base film.The preparation of its film needs first to draw pattern enters again
Row printing, prepares complexity, is not appropriate for use of large-scale production.
The content of the invention
For the complex manufacturing technology of current bipolar electrode presence, conducting particles skewness, easily there is hole
The problems such as, the present invention provides a kind of bipolar electrode.
In order to realize foregoing invention purpose, the technical scheme of the embodiment of the present invention is as follows：
A kind of bipolar electrode, including collector, the collector have just relative first surface and second surface；
Also include outwards folding the first conductive layer set, positive-active layer successively from the first surface；
And the second conductive layer set, negative electrode active layer are outwards folded successively from the second surface；
Also include first conductive layer, collector, the second conductive layer carrying out firm fluid sealant, the fluid sealant is folded
Located at first conductive layer, collector, the second conductive layer surface, and thickness on first conductive layer surface with
The thickness of the positive-active layer is identical, the thickness phase of thickness and negative electrode active layer on second conductive layer surface
Together.
The above-mentioned bipolar electrode that the present invention is provided, uniformly coats one layer of conductive layer, both on bipolar current collector surface
Using resin in collection liquid surface one layer of barrier film of formation, the hole that collector is likely to occur is blocked, electrolyte permeability is prevented
Generation short circuit；The surface of collector is evenly distributed in using the conductive agent in conductive layer again, bipolarity collection is not only increased
The uniformity of flow surface distribution of charges, while the contact resistance between positive and negative electrode material and afflux is also greatly lowered, and energy
Improve the adhesive ability of positive electrode and collector, negative material and collector.
Further, the present invention also provides a kind of lithium ion battery.
A kind of lithium ion battery, including bipolar electrode, the barrier film for isolating the bipolar electrode both positive and negative polarity, electrolysis
Liquid and battery case, the bipolar electrode are bipolar electrode as described above；The barrier film is Kynoar-hexafluoro third
The mixed glue barrier film of alkene barrier film, Kynoar-hexafluoropropene/ceramic complexes barrier film, ceramics.
The above-mentioned lithium ion battery that the present invention is provided, due to uniformly coating one layer of conduction on bipolar current collector surface
Layer, both prevented electrolyte permeability from occurring short circuit using resin in collection liquid surface one layer of barrier film of formation；Again using conduction
Conductive agent in layer is evenly distributed in the surface of collector, not only increases the uniform of bipolar current collector surface charge distribution
Property, while the contact resistance between positive/negative material and afflux is also greatly lowered, and energy of attachment between the two can be improved
Power, when being assembled into battery, can effectively improve battery performance；Because barrier film is used containing Kynoar-hexafluoropropene (P
(VDF-HFP) coating barrier film), by heating hot cold-press process by P (VDF-HFP) gelation, reduces free state electrolyte, from
And reduce the possibility that liquid connects short circuit；In addition, the fluid sealant at bipolar current collector edge is by hot sealing, bipolarity afflux is prevented
The short circuit of body marginal portion, increases the security of battery.
Further, the preparation method that the present invention also provides the lithium ion battery.
The preparation method of lithium ion battery as described above, at least comprises the following steps：
Electrocondution slurry is respectively coated in clean collector first surface and second surface, drying processing obtains folded set
In the first conductive layer and the second conductive layer for being stacked at the second surface of the first surface；
Anode sizing agent is coated on first conductive layer surface, through drying process, obtains being stacked at first conduction
The positive-active layer of layer surface；
Cathode size is coated on second conductive layer surface, through drying process, obtains being stacked at second conduction
The negative electrode active layer of layer surface；
In first conductive layer, the second conductive layer and the collector edge coating fluid sealant, the fluid sealant is in institute
State the thickness thickness identical and in second conductive layer surface with the thickness of positive-active layer of the first conductive layer surface
Spend identical with the thickness of negative electrode active layer；By roller process, bipolar electrode is obtained；
The bipolar electrode and dividing plate are overlapped processing in the way of positive pole-barrier film-negative pole, during overlap-add procedure
Electrolyte is injected to dividing plate, then fluid sealant described in hot-pressing processing, obtain pole group；
Pole group is loaded into packaging film；The battery after encapsulation is completed, 24-48h is stood in 45-60 DEG C of environment；
Battery after shelving carries out chemical conversion treatment according to normal process；Carried out before chemical conversion or to the battery after chemical conversion
Hot cold pressing treatment, hot pressing temperature is 35-90 DEG C during the hot cold pressing treatment, and pressure is 0.1-10MPa, and temperature of colding pressing is 5-20
DEG C, pressure is 0.1-10MPa.
The preparation method for the lithium ion battery that the present invention is provided, because barrier film is used containing Kynoar-hexafluoro
The coating barrier film of propylene (P (VDF-HFP)), by heating hot cold-press process by P (VDF-HFP) gelation, reduces free state electricity
Liquid is solved, so as to reduce the possibility that liquid connects short circuit；And hot sealing is carried out to the fluid sealant at bipolar current collector edge, prevent double
The short circuit of polarity collector marginal portion, improves the security of battery, and whole preparation method technique is simple, is adapted to extensive raw
Production.
Brief description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing：
Fig. 1 is the front view of bipolar electrode provided in an embodiment of the present invention；
Fig. 2 is the A-A sectional views of bipolar electrode provided in an embodiment of the present invention；
Fig. 3 is the part B partial enlarged drawing of bipolar electrode provided in an embodiment of the present invention；
Fig. 4 is the schematic diagram that bipolar electrode provided in an embodiment of the present invention is assembled into lithium ion cell electrode group；
Wherein, 1- collectors；The conductive layers of 2- first, 21- conductive agents, 22- binding agents；The conductive layers of 3- second；4- positive poles are lived
Property layer；5- negative electrode actives layer；6- fluid sealants；7- barrier films.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
As shown in Figures 1 to 3, present example provides a kind of bipolar electrode, including collector 1, and collector 1 has just
Relative first surface and second surface；
Also include outwards folding the first conductive layer 2 set, positive-active layer 4 successively from the first surface；
And the second conductive layer 3 set, negative electrode active layer 5 are outwards folded successively from the second surface；
Also include first conductive layer 2, collector 1, the second conductive layer 3 carrying out firm fluid sealant 6.
Specifically, the fluid sealant 6 is stacked at first conductive layer 2, collector 1, the surface of the second conductive layer 3, and
And the thickness on the surface of the first conductive layer 2 is identical with the thickness of positive-active layer 4, in second conductive layer 3
Thickness on surface is identical with the thickness of negative electrode active layer 5.
Preferably, in order to avoid positive-active layer 4 and negative electrode active layer 5 contact with each other and are likely to result in short circuit, collector 1
Area be respectively greater than positive-active layer 4 and negative electrode active layer 5.
That is, during coating positive-active layer 4, the edge surrounding of the first surface of collector 1 reserves subregion, in advance
The subregion positive-active layer 4 reserved is not covered with；Similarly, during coating negative electrode active layer 5, the second surface of collector 1
The same reserved part region of edge surrounding, the subregion negative electrode active layer 5 reserved can not be covered.The region reserved is used for
Fluid sealant 6 is coated, therefore, fluid sealant 6 covers the edge of the first surface and covers the edge of the second surface so that close
Sealing 6 forms " recessed " the type structure for being fastened on the edge of collector 1, specific as shown in Figure 2.
It is further preferred that during in order to avoid bipolar electrode being assembled into battery, positive-active layer 4 and negative electrode active layer
5 contact and cause short circuit and avoid the occurrence of the bad phenomenons such as analysis lithium, and the area of positive-active layer 4 is less than negative electrode active layer 5
Area.Shown in fig. 2 is that the length in 4 section of positive-active layer is less than the length in 5 section of negative electrode active layer.
Preferably, collector 1 is any in aluminium foil, copper foil, nickel foil, stainless steel foil, aluminium nickel composite insulating foil, aluminum bronze composite insulating foil
Kind.
Preferably, the thickness of collector 1 is 1 μm~40 μm.
Preferably, the thickness of the first conductive layer 2 is 0.1 μm~10.0 μm.
Preferably, the thickness of the second conductive layer 3 is 0.1 μm~10.0 μm.
Preferably, first conductive layer 2, the second conductive layer 3 are formed by electrocondution slurry coating, and the first conductive layer
2 electrocondution slurry is identical with the electrocondution slurry of the second conductive layer 3.
Preferably, counted according to quality 100%, the electrocondution slurry is made up of following component：
Conductive agent 0.1-15%；
Binding agent 1-10%；
Balance of solvent.
Above-mentioned electrocondution slurry is coated on behind the first conductive layer 2 and the surface of the second conductive layer 3, by drying process, obtain as
Surface micro-structure shown in Fig. 3.Wherein 21 be conductive agent, and 22 be binding agent.
Preferably, conductive agent 21 can be at least one of graphite, carbon black, CNT, carbon fiber, graphene；It is viscous
It is at least one of polyvinyl alcohol, acid polyethylene, Kynoar, epoxy resin, phenolic resin, polyurethane to tie agent 22；It is molten
Agent is deionized water or 1-METHYLPYRROLIDONE, and solvent plays a part of dissolving conductive agent and binding agent, dried in smear
Cheng Zhong, solvent volatilization.
Preferably, the positive electrode in positive-active layer 4 is cobalt acid lithium, LiMn2O4, cobalt nickel lithium manganate ternary material, nickel cobalt
At least one of aluminium ternary material, rich lithium manganese, LiFePO4.
Preferably, the pond negative material in negative electrode active layer 5 be Delanium, it is native graphite, carbonaceous mesophase spherules, hard
One or more in carbon, silicon-carbon, silica, metal alloy negative pole.
The bipolar electrode of the above-mentioned offer of the present invention, due to uniformly coating one layer of conduction on bipolar current collector surface
Layer, both prevented electrolyte permeability from occurring short circuit using resin in collection liquid surface one layer of barrier film of formation；Again using conduction
Conductive agent in layer is evenly distributed in the surface of collector, not only increases the uniform of bipolar current collector surface charge distribution
Property, while the contact resistance between positive and negative electrode material and afflux is also greatly lowered, and can improve positive electrode and collector,
Adhesive ability between negative material and collector, when the bipolar electrode that the present invention is provided is assembled into lithium ion battery, energy
It is effectively improved battery performance.
The present invention is on the premise of above-mentioned bipolar electrode is provided, further, and the present invention also provides a kind of lithium-ion electric
Pond.
In one embodiment, a kind of lithium ion battery, including it is bipolar electrode, positive and negative for isolating the bipolar electrode
Barrier film, electrolyte and the battery case of pole, the bipolar electrode are bipolar electrode as described above；The barrier film is poly- inclined
Any in the mixed glue barrier film of PVF-hexafluoropropene barrier film, Kynoar-hexafluoropropene/ceramic complexes barrier film, ceramics
Kind.
The above-mentioned lithium ion battery that the present invention is provided, due to uniformly coating one layer of conduction on bipolar current collector surface
Layer, both prevented electrolyte permeability from occurring short circuit using resin in collection liquid surface one layer of barrier film of formation；Again using conduction
Conductive agent in layer is evenly distributed in the surface of collector, not only increases the uniform of bipolar current collector surface charge distribution
Property, while the contact resistance between positive/negative material and afflux is also greatly lowered, and energy of attachment between the two can be improved
Power, when being assembled into lithium ion battery, can effectively improve battery performance；Because the barrier film of lithium ion battery is used containing poly- inclined
The coating barrier film of PVF-hexafluoropropene (P (VDF-HFP)), such as Kynoar-hexafluoropropene barrier film, Kynoar-six
The mixed glue barrier film of fluoropropene/ceramic complexes barrier film, ceramics, in hot cold pressing treatment, heats hot cold-press process by P (VDF-HFP)
Gelation, reduces free state electrolyte, so as to reduce the possibility that liquid connects short circuit；In addition, the fluid sealant at bipolar current collector edge
By hot sealing, the short circuit of bipolar current collector marginal portion is prevented, the security of battery is improved.
Further, present invention also offers a kind of preparation method of above-mentioned lithium ion battery.
In one embodiment, the preparation method of above-mentioned lithium ion battery comprises the following steps：
(1) making of bipolar electrode：Electrocondution slurry is respectively coated in clean collector first surface and second surface,
Drying processing, obtains being stacked at the first conductive layer of the first surface and is stacked at the second conduction of the second surface
Layer；
Anode sizing agent is coated on first conductive layer surface, through drying process, obtains being stacked at first conduction
The positive-active layer of layer surface；
Cathode size is coated on second conductive layer surface, through drying process, obtains being stacked at second conduction
The negative electrode active layer of layer surface；
In first conductive layer, the second conductive layer and the collector edge coating fluid sealant, the fluid sealant is in institute
State the thickness thickness identical and in second conductive layer surface with the thickness of positive-active layer of the first conductive layer surface
Spend identical with the thickness of negative electrode active layer；By roller process, bipolar electrode is obtained.
(2) bipolar electrode is assembled into lithium ion battery：By bipolarity electricity in the way of positive pole-barrier film-negative pole
Pole and dividing plate are overlapped processing, inject traditional lithium-ion battery electrolyte to dividing plate during overlap-add procedure, then hot-pressing processing institute
Fluid sealant is stated, pole group is obtained, as shown in Figure 4；Pole group is loaded into packaging film；The battery after encapsulation is completed, in 45-60 DEG C of ring
Border stands 24-48h.
(3) lithium ion battery chemical conversion and other subsequent treatments：By the battery after above-mentioned shelve according to normal process
Into processing；Hot cold pressing treatment is carried out before chemical conversion or to the battery after chemical conversion, hot pressing temperature is during the hot cold pressing treatment
35-90 DEG C, pressure is 0.1-10MPa, and temperature of colding pressing is 5-20 DEG C, and pressure is 0.1-10MPa.
Specifically, during the assembling of above-mentioned lithium ion battery, the barrier film used be Kynoar-hexafluoropropene barrier film, it is poly- partially
Any of mixed glue barrier film of PVF-hexafluoropropene/ceramic complexes barrier film, ceramics.This several barrier film can reduce electrolysis
By the infiltration of the hole of collector short circuit occurs for liquid, and can give birth to and be swelled after hot-pressing processing, with positive-active layer, negative electrode active layer
Binding agent in work is crosslinked, by being cold-pressed P (VDF-HFP) gelation, reaches the effect for reducing free state electrolyte.
Preferably, the time of the hot-pressing processing is 1-10min；The time of the cold pressing treatment is 1-10min.
The preparation method of lithium ion battery provided in an embodiment of the present invention, due to uniformly being applied on bipolar current collector surface
One layer of conductive layer is covered, both prevented electrolyte permeability from occurring short circuit in collection liquid surface one layer of barrier film of formation using resin；Again
The surface of collector is evenly distributed in using the conductive agent in conductive layer, bipolar current collector surface charge is not only increased
The uniformity of distribution, while the contact resistance between positive/negative material and afflux is also greatly lowered, and can be improved between the two
Adhesive ability, when being assembled into lithium ion battery, can effectively improve battery performance；Because barrier film is used containing polyvinylidene fluoride
The coating barrier film of alkene-hexafluoropropene (P (VDF-HFP)), by heating hot cold-press process by P (VDF-HFP) gelation, reduces trip
Amorph electrolyte, so as to reduce the possibility that liquid connects short circuit；And hot sealing is carried out to the fluid sealant at bipolar current collector edge,
The short circuit of bipolar current collector marginal portion is prevented, the security of battery is improved, whole preparation method technique is simple, is adapted to big rule
Mould is produced.
For the lithium for better illustrating the technical scheme of bipolar electrode of the present invention and being made by the bipolar electrode
The technical scheme of ion battery, the principle of lithium ion battery is illustrated below by way of multiple embodiments, acts on and reaches
Effect.
Embodiment 1
A kind of lithium ion battery, its preparation method is as follows
(1) making of electrocondution slurry
Counted according to quality 100%, electrocondution slurry is
Carbon black (SP) 2%；
Epoxy resin 4%；
Nmp solvent 94%；
Above-mentioned recipe ingredient is mixed into electrocondution slurry.
(2) making of bipolar electrode：
As shown in Fig. 2 using 20 μm of Copper-Aluminum compound foils as the collector 1 of bipolar electrode, by the conductive paste of step (1)
Material is uniformly coated in the tow sides of collector according to certain surface density, and drying obtains the first conductive layer 2 and second conductive
Layer 3
Will be by positive active material LiCoO2, conductive agent SP, binding agent PVDF be mixed in NMP stirrings obtain it is finely dispersed just
Pole slurry, is coated on the surface for scribbling the first conductive layer 2, notes blanking in advance close to the surface at edge in the first conductive layer 2, dries
It is dry, obtain positive-active layer 4；
Then it will be mixed in water and stirred by negative electrode active material Delanium, conductive agent SP, binding agent SBR, thickener CMC
Finely dispersed cathode size is obtained, the surface for scribbling the second conductive layer 3 is coated on, noted in the second conductive layer 3 close to edge
Surface blank in advance, dry, obtain negative electrode active layer 5；
Bipolar electrode is obtained after roll-in；It is reserved at bipolar current collector edge and the first conductive layer 2 and the second conductive layer 3
Lay edges at coat fluid sealant 6, dry, obtain bipolar electrode；
(3) assembling of lithium ion battery：
Such as Fig. 4, placing area is all higher than the P than positive-active layer 4, negative electrode active layer 5 between adjacent both positive and negative polarity
(VDF-HFP) barrier film 7, add electrolyte, are superimposed as 4 layers, wherein one end is the electrode of only positive pole, and the other end only has negative pole
Electrode；Battery core is sealed by the fluid sealant 6 at hot pressing edge；Then battery core is fitted into wrapping film, battery core shelves 45 DEG C of rings
Border stands 36h, and with first hot pressing 2min, the pressure 0.2MPa at 80 DEG C of hot cold press, 2min, pressure are then cold-pressed at 18 DEG C
0.2MPa, obtains condensed state battery, is melted into, then it is 14.8V, mark to obtain nominal voltage by last wrapping film sealing
Capacity is called 90mAh bipolarity lithium ion battery.
Embodiment 2
A kind of lithium ion battery, its preparation method is as follows
(1) making of electrocondution slurry
Counted according to quality 100%, electrocondution slurry is
Carbon black (SP) 2%；
Epoxy resin 4%；
Nmp solvent 94%
Above-mentioned recipe ingredient is mixed into electrocondution slurry.
(2) making of bipolar electrode：
As shown in Fig. 2 using 20 μm of Copper-Aluminum compound foils as the collector 1 of bipolar electrode, by the conductive paste of step (1)
Material is uniformly coated in the tow sides of collector according to certain surface density, and drying obtains the first conductive layer 2 and second conductive
Layer 3
Will be by positive active material LiCoO2, conductive agent SP, binding agent PVDF be mixed in NMP stirrings obtain it is finely dispersed just
Pole slurry, is coated on the surface of the first conductive layer 2, notes blanking in advance close to the surface at edge in the first conductive layer 2, drying,
Obtain positive-active layer 4；
Then it will be mixed in water and stirred by negative electrode active material Delanium, conductive agent SP, binding agent SBR, thickener CMC
Finely dispersed cathode size is obtained, the surface for scribbling the second conductive layer 3 is coated on, noted in the second conductive layer 3 close to edge
Surface blank in advance, dry, obtain negative electrode active layer 5；
Bipolar electrode is obtained after roll-in；It is reserved at bipolar current collector edge and the first conductive layer 2 and the second conductive layer 3
Lay edges at coat fluid sealant 6, dry, obtain bipolar electrode；
(3) assembling of lithium ion battery：
Such as Fig. 4, placing area is all higher than the P than positive-active layer 4, negative electrode active layer 5 between adjacent both positive and negative polarity
(VDF-HFP) barrier film 7, add electrolyte, are superimposed as 4 layers, wherein one end is the electrode of only positive pole, and the other end only has negative pole
Electrode；Battery core is sealed by the fluid sealant 6 at hot pressing edge；Then battery core is fitted into wrapping film, battery core shelves 45 DEG C of rings
Border stands 36h, is then melted into battery core, chemical conversion terminates, with the first hot pressing 2min, pressure at 80 DEG C of hot cold press
0.2MPa, is then cold-pressed 2min, pressure 0.2MPa at 18 DEG C, obtains condensed state battery, then close by last wrapping film
It is the bipolarity lithium ion battery that 14.8V, nominal capacity are 90mAh that envelope, which obtains nominal voltage,.
Embodiment 3
A kind of lithium ion battery, its preparation method is as follows
(1) making of electrocondution slurry
Counted according to quality 100%, electrocondution slurry is
Carbon black (SP) 2%；
Kynoar 4%；
Nmp solvent 94%；
Above-mentioned recipe ingredient is mixed into electrocondution slurry.
(2) making of bipolar electrode：
As shown in Fig. 2 using 16 μm of aluminium foils as the collector 1 of bipolar electrode, by the electrocondution slurry of step (1) according to
Certain surface density is uniformly coated in the tow sides of collector, drying, obtains the first conductive layer 2 and the second conductive layer 3
Will be by positive active material LiNi0.5Co0.2Mn0.3O2, conductive agent CNTs, binding agent PVDF be mixed in NMP stirrings and obtain
Finely dispersed anode sizing agent, is coated on the surface for scribbling the first conductive layer 2, notes the table close to edge in the first conductive layer 2
Face blanks in advance, drying, obtains positive-active layer 4；
Then will be by negative electrode active material Li4Ti5O12, conductive agent SP, binding agent SBR, thickener CMC be mixed in water and stir
Finely dispersed cathode size is obtained, the surface for scribbling the second conductive layer 3 is coated on, noted in the second conductive layer 3 close to edge
Surface blank in advance, dry, obtain negative electrode active layer 5；
Bipolar electrode is obtained after roll-in；It is reserved at bipolar current collector edge and the first conductive layer 2 and the second conductive layer 3
Lay edges at coat fluid sealant 6, dry, obtain bipolar electrode；
(3) assembling of lithium ion battery：
Such as Fig. 4, placing area is all higher than the P than positive-active layer 4, negative electrode active layer 5 between adjacent both positive and negative polarity
(VDF-HFP) barrier film 7, add electrolyte, are superimposed as 4 layers, have 4 layers of positive pole, 4 layers of negative pole, wherein one end is only positive pole
Electrode, the other end only has the electrode of negative pole；Battery core is sealed by the fluid sealant 6 at hot pressing edge；Then battery core is loaded into outsourcing
Fill in film, battery core shelves 45 DEG C of environment and stands 36h, with first hot pressing 2min, the pressure 0.2MPa at 80 DEG C of hot cold press, then exist
2min, pressure 0.2MPa are cold-pressed at 18 DEG C, condensed state battery is obtained, is melted into, then is sealed by last wrapping film
It is the bipolarity lithium ion battery that 9.6V, nominal capacity are 65mAh to nominal voltage.
Embodiment 4
A kind of lithium ion battery, its preparation method is as follows
(1) making of electrocondution slurry
Counted according to quality 100%, electrocondution slurry is
CNTs 1%；
Kynoar 3%；
Nmp solvent 96%；
Above-mentioned recipe ingredient is mixed into electrocondution slurry.
(2) making of bipolar electrode：
As shown in Fig. 2 using 16 μm of aluminium foils as the collector 1 of bipolar electrode, by the electrocondution slurry of step (1) according to
Certain surface density is uniformly coated in the tow sides of collector, drying, obtains the first conductive layer 2 and the second conductive layer 3
Will be by positive active material LiNi0.5Co0.2Mn0.3O2, conductive agent CNTs, binding agent PVDF be mixed in NMP stirrings and obtain
Finely dispersed anode sizing agent, is coated on the surface for scribbling the first conductive layer 2, notes the table close to edge in the first conductive layer 2
Face blanks in advance, drying, obtains positive-active layer 4；
Then will be by negative electrode active material Li4Ti5O12, conductive agent SP, binding agent SBR, thickener CMC be mixed in water and stir
Finely dispersed cathode size is obtained, the surface for scribbling the second conductive layer 3 is coated on, noted in the second conductive layer 3 close to edge
Surface blank in advance, dry, obtain negative electrode active layer 5；
Bipolar electrode is obtained after roll-in；It is reserved at bipolar current collector edge and the first conductive layer 2 and the second conductive layer 3
Lay edges at coat fluid sealant 6, dry, obtain bipolar electrode；
(3) assembling of lithium ion battery：
Such as Fig. 4, placing area is all higher than the P than positive-active layer 4, negative electrode active layer 5 between adjacent both positive and negative polarity
(VDF-HFP) barrier film 7, add electrolyte, are superimposed as 4 layers, have 4 layers of positive pole, 4 layers of negative pole, wherein one end is only positive pole
Electrode, the other end only has the electrode of negative pole；Battery core is sealed by the fluid sealant 6 at hot pressing edge；Then battery core is loaded into outsourcing
Fill in film, battery core shelves 45 DEG C of environment and stands 36h, is melted into；With the first hot pressing 10min at 80 DEG C of hot cold press after chemical conversion,
Pressure 0.3MPa, is then cold-pressed 10min, pressure 0.3MPa at 18 DEG C, obtains condensed state battery, then by last outer packing
It is the bipolarity lithium ion battery that 9.6V, nominal capacity are 65mAh that film sealing, which obtains nominal voltage,.
Comparative example 1：
Foil used in control group bipolar electrode is not have cated conventional foil, barrier film to be conventional PE basement membranes,
Other preparation conditions are consistent with embodiment 1.Nominal voltage is that 14.8V, nominal capacity are 90mAh.
Comparative example 2：
Foil used in control group bipolar electrode is not have cated conventional foil, barrier film to be conventional PE basement membranes,
Other preparation conditions are consistent with embodiment 4.Battery nominal voltage is that 9.6V, nominal capacity are 65mAh.
The internal resistance of lithium ion battery prepared by above example 1~4 and comparative example 1~2, whether leakage, self discharge are big
It is small to be counted, as described in Table 1.
Wherein self discharge method of testing is：Battery first charges to half electric state, and measurement obtains a magnitude of voltage V1, then normal temperature
72h is shelved, then measures and obtains a magnitude of voltage V2, self discharge K=(V1-V2)/72.
The embodiment 1~4 of table 1 and the battery performance test data of comparative example 1~2
| Example | Internal resistance | Whether leakage | Self discharge K values |
| Embodiment 1 | 3.1mΩ | It is no | 0.082mV/h |
| Embodiment 2 | 2.8mΩ | It is no | 0.073mV/h |
| Embodiment 3 | 2.9mΩ | It is no | 0.057mV/h |
| Embodiment 4 | 3.0mΩ | It is no | 0.065mV/h |
| Comparative example 1 | 4.8mΩ | It is unobvious | 0.180mV/h |
| Comparative example 2 | 5.2mΩ | It is unobvious | 0.242mV/h |
As known from Table 1, using the foil of conductive coating and the painting containing Kynoar-hexafluoropropene (P (VDF-HFP))
Cover barrier film, by heating hot cold-press process by P (VDF-HFP) gelation, can effectively reduce internal resistance, reduce leakage risk,
Prepared self-discharge of battery is small.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., all should be included within protection scope of the present invention.
Claims (10)
1. a kind of bipolar electrode, including collector, it is characterised in that：The collector has just relative first surface and the
Two surfaces；
Also include outwards folding the first conductive layer set, positive-active layer successively from the first surface；
And the second conductive layer set, negative electrode active layer are outwards folded successively from the second surface；
Also include first conductive layer, collector, the second conductive layer carrying out firm fluid sealant, the fluid sealant is stacked at
First conductive layer, collector, the surface of the second conductive layer, and thickness on first conductive layer surface with it is described
The thickness of positive-active layer is identical, and the thickness on second conductive layer surface is identical with the thickness of negative electrode active layer.
2. bipolar electrode as claimed in claim 1, it is characterised in that：First conductive layer, the second conductive layer are by conduction
Slurry coating is formed.
3. bipolar electrode as claimed in claim 2, it is characterised in that：Counted according to quality 100%, the electrocondution slurry is by such as
The following group is grouped into：
Conductive agent 0.1-15%；
Binding agent 1-10%
Balance of solvent.
4. bipolar electrode as claimed in claim 3, it is characterised in that：The conductive agent be graphite, carbon black, CNT,
At least one of carbon fiber, graphene；The bonding agent be polyvinyl alcohol, acid polyethylene, Kynoar, epoxy resin,
At least one of phenolic resin, polyurethane；The solvent is deionized water or 1-METHYLPYRROLIDONE.
5. bipolar electrode as claimed in claim 1, it is characterised in that：The thickness of first conductive layer be 0.1 μm~
10.0μm；And/or the thickness of second conductive layer is 0.1 μm~10.0 μm.
6. bipolar electrode as claimed in claim 1, it is characterised in that：The fluid sealant is polypropylene, maleic anhydride grafting
Any of polypropylene, modified poly ethylene.
7. bipolar electrode as claimed in claim 1, it is characterised in that：The collector is aluminium foil, copper foil, nickel foil, stainless
Any of steel foil, aluminium nickel composite insulating foil, aluminum bronze composite insulating foil；The thickness of the collector is 1 μm~40 μm.
8. a kind of lithium ion battery, including bipolar electrode, barrier film, electrolyte for isolating the bipolar electrode both positive and negative polarity
And battery case, it is characterised in that：The bipolar electrode is the bipolar electrode described in any one of claim 1~7；It is described
Barrier film be Kynoar-hexafluoropropene barrier film, Kynoar-hexafluoropropene/ceramic complexes barrier film, the mixed glue of ceramics every
Film.
9. the preparation method of lithium ion battery as claimed in claim 7, it is characterised in that at least comprise the following steps：
Electrocondution slurry is respectively coated in clean collector first surface and second surface, drying processing obtains being stacked at institute
State the first conductive layer of first surface and be stacked at the second conductive layer of the second surface；
Anode sizing agent is coated on first conductive layer surface, through drying process, obtains being stacked at the first conductive layer table
The positive-active layer in face；
Cathode size is coated on second conductive layer surface, through drying process, obtains being stacked at the second conductive layer table
The negative electrode active layer in face；
In first conductive layer, the second conductive layer and the collector edge coating fluid sealant, the fluid sealant is described
The thickness of the thickness of one conductive layer surface and the positive-active layer it is identical and second conductive layer surface thickness with
The thickness of the negative electrode active layer is identical；By roller process, bipolar electrode is obtained；
The bipolar electrode and dividing plate are overlapped processing in the way of positive pole-barrier film-negative pole, during overlap-add procedure to every
Plate injects electrolyte, then fluid sealant described in hot-pressing processing, obtains pole group；
Pole group is loaded into packaging film；The battery after encapsulation is completed, 24-48h is stood in 45-60 DEG C of environment；
Battery after shelving carries out chemical conversion treatment according to normal process；Heat is carried out to the battery before chemical conversion or after chemical conversion cold
Pressure processing, hot pressing temperature is 35-90 DEG C during the hot cold pressing treatment, and pressure is 0.1-10MPa, and temperature of colding pressing is 5-20 DEG C, pressure
Power is 0.1-10MPa.
10. the preparation method of lithium ion battery as claimed in claim 9, it is characterised in that：The time of the hot-pressing processing is
1-10min；The time of the cold pressing treatment is 1-10min.
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