CN109860603A - Lithium battery pole slice and preparation method thereof and lithium battery - Google Patents
Lithium battery pole slice and preparation method thereof and lithium battery Download PDFInfo
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- CN109860603A CN109860603A CN201910054264.8A CN201910054264A CN109860603A CN 109860603 A CN109860603 A CN 109860603A CN 201910054264 A CN201910054264 A CN 201910054264A CN 109860603 A CN109860603 A CN 109860603A
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- 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 lithium battery pole slice and preparation method thereof and lithium battery, belong to technical field of lithium batteries, concrete scheme is as follows: a kind of lithium battery pole slice, including metallic framework and active material, the metallic framework has open structure, the active material is embedded in the open structure of metallic framework, and there are gaps between the metallic framework and active material；A kind of lithium battery including diaphragm, electrolyte and anode pole piece containing positive active material and contains the cathode pole piece of negative electrode active material.The beneficial effects of the invention are as follows by increase pole piece thickness battery energy density can be improved, while again guarantee battery have good high rate performance and cycle performance.
Description
Technical field
The invention belongs to technical field of lithium batteries, and in particular to lithium battery pole slice and preparation method thereof and lithium battery.
Background technique
Lithium battery is a kind of very widely used battery.The structure of current positive (negative) pole piece of lithium battery be all one layer just
The mixture of (negative) pole active material and conductive agent, binder is covered on positive (negative) pole collector, and preparation method is as follows: first
Positive (negative) pole active material and conductive agent, binder, solvent are mixed into slurry, then slurry is coated on positive (negative) pole collector
On, last dry out solvent is simultaneously compacted pole piece.
Requirement with market to battery energy density is continuously improved, and the various methods for improving battery energy density all obtain
Research extensively, wherein having a kind of important method for improving battery energy density is the thickness for increasing electrode.However it is limited to tradition
Pole piece structure electron conduction it is bad and electrolyte diffusion admittance is few, the increase of pole piece thickness will influence to a certain extent
The increase of the high rate performance and cycle performance of battery, especially cathode thickness also will increase the safety of pole piece analysis lithium afterwards to a certain extent
Risk.
Summary of the invention
The purpose of the invention is to provide a kind of lithium battery pole slice, the energy density of lithium battery can be improved, and guarantee electricity
Pond has good high rate performance and cycle performance.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of lithium battery pole slice, the lithium battery pole slice include metallic framework and active material, and the metallic framework, which has, to be opened
Property structure, the active material are embedded in the open structure of metallic framework, deposit between the metallic framework and active material
In gap.
Further, the active material is positive active material or negative electrode active material.
Further, the positive active material is cobalt acid lithium, lithium nickelate, spinel lithium manganate, layered lithium manganate, nickel cobalt
Binary material, nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiFePO4, spinel nickel LiMn2O4, lithium-rich manganese base material,
At least one of transition metal oxide, transition metal phosphate；The negative electrode active material be graphite, hard charcoal, soft charcoal, in
Between phase carbosphere, lithium titanate, nano-silicon negative electrode material, silicon-carbon composite cathode material, aoxidize in sub- silicium cathode material at least one
Kind.
Further, the lithium battery pole slice with a thickness of 0.05 ~ 10 mm.
The preparation method of above-mentioned lithium battery pole slice, steps are as follows:
Step 1: a certain amount of larger molecular organics are first dissolved in formation larger molecular organics solution among solvent, wherein greatly
The mass fraction of molecular organic is 0.1 ~ 99.9%；
Step 2: metal material, active material, larger molecular organics solution are stirred into slurry according to a certain percentage,
By slurry coating film forming, obtain after solvent volatilization with a thickness of the diaphragm of 0.05 ~ 10 mm, in the diaphragm, the metal material
Mass fraction be 5 ~ 60%, the mass fractions of larger molecular organics is 0.1 ~ 20%, and surplus is the mass fraction of active material；
Step 3: first by diaphragm, 0.5 ~ 4h of high-temperature calcination removes big point at 300 ~ 600 DEG C under inert gas or nitrogen protection
Sub- organic matter, then M ± 50 DEG C are raised the temperature to, it is kept for 0.1 ~ 6000 second for metallic material, is had after cooling solidification
There is the metallic framework of open structure, be filled with active material in the metallic framework, lithium battery pole slice is made, wherein M is gold
Belong to the fusing point of material.
Further, in step 2, the metal material is metal powder and/or metallic fiber, the metal powder
Particle size range be 0.01 ~ 1 μm；The metallic fiber diameter range is 0.01 ~ 5 μm, and length range is 0.05 ~ 100 μm.
Further, in step 2, the metal material be nickel, aluminium, copper, iron, manganese, cobalt, gold, silver, zirconium, zinc, tin,
The combination of one or more of titanium, bismuth.
Further, in step 1, the larger molecular organics be polyethylene glycol oxide (PEO), polyethylene glycol (PEG),
Polypropylene glycol, polyacrylonitrile, Kynoar (PVDF), polyacrylate, sodium carboxymethylcellulose (CMC), gathers polyvinyl alcohol
At least one of vinylpyrrolidone (PVP), polystyrene, surfactant；The solvent is ethyl alcohol, methanol, propyl alcohol, second
Nitrile, acetone, water, N-Methyl pyrrolidone (NMP), n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc),
At least one of toluene.
A kind of lithium battery, the lithium battery include diaphragm, electrolyte, the anode pole piece containing positive active material and contain
The cathode pole piece of negative electrode active material.
Compared with prior art, the present invention has the following advantages and beneficial effects:
A kind of lithium battery pole slice that the present invention records, can be close by increasing the pole piece thickness raising energy content of battery when designing battery
Degree, while guaranteeing it with good high rate performance and cycle performance.
Detailed description of the invention
Fig. 1 is the structural schematic diagram (sectional view) of lithium battery pole slice of the present invention, wherein 1 is active material, 2 be metal bone
Frame, 3 be gap；
Fig. 2 is the cycle performance of the battery of embodiment 1 and comparative example 1, and test condition: 25 DEG C, 1C charging, 1C discharges；
Fig. 3 is the multiplying power discharging property of the battery of embodiment 2, test condition: 25 DEG C, is discharged under the conditions of 0.5C, 1C, 3C, 5C；
Fig. 4 is the multiplying power discharging property of the battery of comparative example 2, test condition: 25 DEG C, is discharged under the conditions of 0.5C, 1C, 3C, 5C；
Fig. 5 is the multiplying power discharging property of the battery of embodiment 3 and comparative example 3, test condition: 25 DEG C, 0.2C, 0.5C, 1C, 3C,
It discharges under the conditions of 5C；
Fig. 6 is the cycle performance of the battery of embodiment 4 and comparative example 4, and test condition: 25 DEG C, 1C charging, 1C discharges.
Specific embodiment
Further description of the technical solution of the present invention for 1-6 and embodiment with reference to the accompanying drawing, but is not limited to
This, all technical solution of the present invention to be modified or equivalent replacement, range without departing from the spirit of the technical scheme of the invention,
It should cover within the protection scope of the present invention.The material and instrument arrived used in the present invention such as not special explanation,
It is commercially available for conventional material and conventional instrument.
Specific embodiment 1:
A kind of lithium battery pole slice, including metallic framework 2 and active material 1, the metallic framework 2 has open structure, described
Active material 1 is embedded in the open structure of metallic framework 2, and there are gaps 3 between the metallic framework 2 and active material 1.
Specifically, the metallic framework 2 forms a continuous overall structure by metal material, while guaranteeing metal bone again
2 structure of frame has opening.The inner space of open skeleton structure is connected to the external world, opposite with open structural framework
What is answered is the skeleton structure of closed, and the skeleton structure inner space of closed is isolated entirely from by skeleton structure just.
Specifically, metallic framework 2 and 1 particle of active material are respectively formed and good contact and formed to 1 particle of active material
Certain restraint stress, but not exclusively package 1 particle of active material of metallic framework 2 is to guarantee that 1 particle of active material is not sealed
It closes.
Further, the active material 1 is positive active material or negative electrode active material, is inlaid with positive active material
Metallic framework be lithium battery anode piece, be inlaid with negative electrode active material metallic framework be lithium battery cathode pole piece.
Preferably, the positive active material is cobalt acid lithium, lithium nickelate, spinel lithium manganate, layered lithium manganate, nickel cobalt two
First material, nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, LiFePO4, spinel nickel LiMn2O4, lithium-rich manganese base material, mistake
Cross at least one of metal oxide, transition metal phosphate；The negative electrode active material is graphite, hard charcoal, soft charcoal, centre
At least one of phase carbosphere, lithium titanate, nano-silicon negative electrode material, silicon-carbon composite cathode material, the sub- silicium cathode material of oxidation.
Further, the lithium battery pole slice with a thickness of 0.05 ~ 10 mm.
A kind of preparation method of lithium battery pole slice, steps are as follows:
Step 1: first a certain amount of larger molecular organics are dissolved among solvent solution is formed, wherein larger molecular organics
Mass fraction is 0.1 ~ 99.9%；
Step 2: metal material, active material, larger molecular organics solution are stirred into slurry according to a certain percentage,
By slurry coating film forming, obtain after solvent volatilization with a thickness of the diaphragm of 0.05 ~ 10 mm, in the diaphragm, the metal material
Quality account for the 5 ~ 60% of diaphragm gross mass, the quality of larger molecular organics accounts for the 0.1 ~ 20% of diaphragm gross mass, and surplus is activity
The mass fraction of substance；The shape and size of diaphragm are unlimited, can require arbitrarily to cut according to cell shapes；
Step 3: first by diaphragm, 0.5 ~ 4h of high-temperature calcination removes big point at 300 ~ 600 DEG C under inert gas or nitrogen protection
Sub- organic matter, then M ± 50 DEG C are raised the temperature to, it is kept for 0.1 ~ 6000 second for metallic material, is had after cooling solidification
There is the metallic framework 2 of open structure, is filled with active material 1 in the metallic framework 2, lithium battery pole slice is made, wherein M is
The fusing point of metal powder or metallic fiber.
Further, in step 2, the metal material is metal powder and/or metallic fiber, the metal powder
Particle size range be 0.01 ~ 1 μm；The metallic fiber diameter range is 0.01 ~ 5 μm, and length range is 0.05 ~ 100 μm.
Preferably, in step 2, the metal material be nickel, aluminium, copper, iron, manganese, cobalt, gold, silver, zirconium, zinc, tin, titanium,
The combination of one or more of bismuth.
Further, the combination of the metal material is mixing or alloy.
Further, in step 1, the larger molecular organics be polyethylene glycol oxide (PEO), polyethylene glycol (PEG),
Polypropylene glycol, polyacrylonitrile, Kynoar (PVDF), polyacrylate, sodium carboxymethylcellulose (CMC), gathers polyvinyl alcohol
At least one of vinylpyrrolidone (PVP), polystyrene, surfactant；The solvent is ethyl alcohol, methanol, propyl alcohol, second
Nitrile, acetone, water, N-Methyl pyrrolidone (NMP), n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc),
At least one of toluene.
A kind of lithium battery including diaphragm, electrolyte and anode pole piece containing positive active material and contains negative electrode active
The cathode pole piece of substance.
Embodiment 1:
First PVDF is dissolved in be configured in NMP 0.1% solution, then it is metallic aluminium powder and commercially available lithium cobaltate cathode is living
Property material powder be added in solution and stir, be mixed into uniform slurry and coating film forming, dry out solvent obtains with a thickness of 10mm's
Diaphragm, wherein the average grain diameter of metallic aluminium powder is 1 μm, and the mass fraction that the mass fraction of metallic aluminium powder accounts for 5%, PVDF accounts for 0.1%；
Again by membrane cutting growth 69mm, wide 45mm, with a thickness of the rectangle lamella of 10 mm；In the case where inert gas argon atmospher is enclosed, by diaphragm
0.5h is calcined at 600 DEG C and removes PVDF, then raises the temperature to 660 DEG C, is kept for 1 second, is obtained lithium cobaltate cathode piece.
First CMC is dissolved in water be configured to 30% solution, then by copper powder and commercially available graphite cathode material
Powder is added in solution and stirs, and is mixed into uniform slurry and coating film forming, and dry out solvent obtains the diaphragm with a thickness of 10mm,
The average grain diameter of middle copper powder is 0.01 μm, and the mass fraction that the mass fraction of copper powder accounts for 60%, CMC accounts for 20%；Again will
Membrane cutting growth 70mm, wide 46mm, the rectangle lamella with a thickness of 10 mm；In the case where inert gas argon atmospher is enclosed, diaphragm is existed
1h is calcined at 400 DEG C and removes CMC, then raises the temperature to 1060 DEG C, is kept for 6000 seconds, is obtained graphite cathode piece.
By above-mentioned positive plate and negative electrode tab collocation commercialization electrolyte and commercialization diaphragm lamination assembling at lithium ion battery,
Test its energy density, multiplying power charging performance, multiplying power discharging property and cycle performance.
Comparative example 1:
Referring to lithium ion battery commodity production method mature at present, by the lithium cobaltate cathode material of model in the same manner as in Example 1
Material collocation conductive black, PVDF binder and solvent NMP are configured to lithium cobaltate cathode slurry and are coated on 10 μm of aluminium foil surfaces,
Then the roll-in under drying, 40 tons of pressure at 120 DEG C, is cut into the positive plate of long 69mm, width 45mm.
Referring to lithium ion battery commodity production method mature at present, by the graphite cathode of model in the same manner as in Example 1
Material adapted conductive black, SBR binder, CMC stabilizer and aqueous solvent are configured to graphite cathode slurry and are coated on 6 μm of copper
Foil surface, the then roll-in under drying, 50 tons of pressure at 100 DEG C, is cut into the negative electrode tab of long 70mm, width 46mm.
By above-mentioned positive plate and negative electrode tab arrange in pairs or groups model in the same manner as in Example 1 commercialization electrolyte and commercialization diaphragm
Lamination assembling tests its energy density, multiplying power charging performance, multiplying power discharging property and cycle performance at lithium ion battery.
Embodiment 2:
PEG and PEO is first configured to 99.9% solution according to the quality of 1:1 than co-dissolve in acetonitrile, then by metal iron powder
It is added in solution and stirs with commercially available lithium iron phosphate positive material powder, be mixed into uniform slurry and coating film forming, dry
Dry solvent obtains the diaphragm with a thickness of 0.05mm, and wherein the average grain diameter of metal iron powder is 0.1 μm, the mass fraction of metal iron powder
It accounts for 10%, PEG and PEO total mass fraction accounts for 2%；Again by membrane cutting growth 69mm, wide 45mm, with a thickness of the rectangular of 0.05 mm
Shape lamella；Under nitrogen atmosphere, diaphragm is calcined to 1h at 500 DEG C and removes PEG and PEO, then raises the temperature to 1538 DEG C, is protected
It holds 0.1 second, obtains iron phosphate lithium positive pole piece.
PVP dissolution is first configured to 5% solution in ethanol, then by metal nickel powder and commercially available silicon-carbon Compound Negative
Pole material powder is added in solution and stirs, and is mixed into uniform slurry and coating film forming, and dry out solvent obtains with a thickness of 0.05 mm
Diaphragm, wherein the average grain diameter of metal nickel powder be 0.5 μm, the mass fraction that the mass fraction of metal nickel powder accounts for 20%, PVP accounts for
3%；Again by membrane cutting growth 70mm, wide 46mm, with a thickness of the rectangle lamella of 0.05 mm；In the case where inert gas argon atmospher is enclosed,
Diaphragm is calcined to 1h at 450 DEG C and removes PVP, then raises the temperature to 1450 DEG C, is kept for 10 seconds, obtains silicon-carbon composite cathode
Piece.
By above-mentioned positive plate and negative electrode tab collocation commercialization electrolyte and commercialization diaphragm lamination assembling at lithium ion battery,
Test its energy density, multiplying power charging performance, multiplying power discharging property and cycle performance.
Comparative example 2:
Referring to lithium ion battery commodity production method mature at present, by the iron phosphate lithium positive pole of model in the same manner as in Example 2
Material adapted conductive black, PVDF binder and solvent NMP are configured to lithium iron phosphate cathode slurry and are coated on 50 μ m-thicks not
It becomes rusty steel mesh surface, then drying, roll-in under 40 tons of pressure, the positive plate for being cut into long 69mm, width 45mm at 130 DEG C.
It is referring to lithium ion battery commodity production method mature at present, the silicon-carbon of model in the same manner as in Example 2 is compound
Negative electrode material collocation conductive black, polyacrylic acid binder, CMC stabilizer and aqueous solvent are configured to silicon-carbon composite cathode slurry
And be coated on 50 μ m-thick nickel screen surfaces, then at 95 DEG C drying, roll-in under 55 tons of pressure, be cut into long 70mm, width 46mm is born
Pole piece.
By above-mentioned positive plate and negative electrode tab arrange in pairs or groups model in the same manner as in Example 2 commercialization electrolyte and commercialization diaphragm
Lamination assembling tests its energy density, multiplying power charging performance, multiplying power discharging property and cycle performance at lithium ion battery.
Embodiment 3:
First polyacrylonitrile is dissolved in be configured in DMF 15% solution, then by metal aluminum fiber and commercially available nickel cobalt manganese three
First positive electrode powder is added in solution and stirs, and is mixed into uniform slurry and coating film forming, dry out solvent obtain with a thickness of
The diaphragm of 0.5mm, wherein the average diameter of metal aluminum fiber is 5 μm, and the average length of metal aluminum fiber is 100 μm, metallic aluminium
The mass fraction of fiber accounts for 15%, and the mass fraction of polyacrylonitrile accounts for 3%；Again by membrane cutting grow up 69mm, width 45mm, with a thickness of
The rectangle lamella of 0.5 mm；Under nitrogen atmosphere, diaphragm is calcined to 1h at 500 DEG C and removes polyacrylonitrile, then by temperature liter
It up to 700 DEG C, is kept for 0.1 second, obtains nickel-cobalt-manganese ternary positive plate.
First polystyrene is dissolved in be configured in toluene 2% solution, then by metal copper fiber and commercially available graphite
Negative electrode material powder is added in solution and stirs, and is mixed into uniform slurry and coating film forming, and dry out solvent obtains with a thickness of 0.5mm
Diaphragm, wherein the average diameter of metal copper fiber is 0.01 μm, and the average length of metal copper fiber is 0.05 μm, and metallic copper is fine
The mass fraction of dimension accounts for 32%, and the mass fraction of polystyrene accounts for 1.5%；Again by membrane cutting grow up 70mm, width 46mm, with a thickness of
The rectangle lamella of 0.5 mm；Under nitrogen atmosphere, diaphragm is calcined to 0.8h at 550 DEG C and removes polystyrene, then by temperature
700 DEG C are increased to, is kept for 0.1 second, obtains graphite cathode piece.
By above-mentioned positive plate and negative electrode tab collocation commercialization electrolyte and commercialization diaphragm lamination assembling at lithium ion battery,
Test its energy density, multiplying power charging performance, multiplying power discharging property and cycle performance.
Comparative example 3:
The nickel-cobalt-manganternary ternary anode material of model in the same manner as in Example 3 is dispersed in solvent NMP, then pressurization pours into
It in the foamed aluminium collector of 0.5mm thickness, is then dried at 125 DEG C, is cut into the positive plate of long 69mm, width 45mm.
The graphite cathode material of model in the same manner as in Example 3 is dispersed in solvent NMP, then pressurization pours into 0.5mm
In thick foam copper current collector, is then dried at 105 DEG C, be cut into the negative electrode tab of long 70mm, width 46mm.
By above-mentioned positive plate and negative electrode tab arrange in pairs or groups model in the same manner as in Example 3 commercialization electrolyte and commercialization diaphragm
Lamination assembling tests its energy density, multiplying power charging performance, multiplying power discharging property and cycle performance at lithium ion battery.
Embodiment 4:
First polyacrylate is dissolved in be configured in NMP 10% solution, then by metal aluminum fiber and commercially available nickel cobalt manganese
Tertiary cathode material powder is added in solution and stirs, and is mixed into uniform slurry and coating film forming, and dry out solvent obtains with a thickness of 1
The diaphragm of mm, wherein the average diameter of metal aluminum fiber is 1 μm, and the average length of metal aluminum fiber is 10 μm, metal aluminum fiber
Mass fraction account for 18%, the mass fraction of polyacrylate accounts for 8%；Again by membrane cutting growth 69mm, wide 45mm, with a thickness of 1 mm
Rectangle lamella；Under nitrogen atmosphere, diaphragm is calcined to 3h at 520 DEG C and removes polyacrylate, then is raised the temperature to
It 659 DEG C, is kept for 2 seconds, obtains nickel-cobalt-manganese ternary positive plate.
Polypropylene glycol dissolution is first configured to 55% solution in acetone, then by metal copper fiber, metal cu-zn alloy powder
It is added in solution and stirs with commercially available graphite cathode material powder, be mixed into uniform slurry and coating film forming, dry molten
Agent obtains the diaphragm with a thickness of 1mm, and wherein the average diameter of metal copper fiber is 0.09 μm, and the average length of metal copper fiber is
0.8 μm, the mass fraction of metal copper fiber accounts for 8%, and the average grain diameter of metal cu-zn alloy powder is 0.1 μm, metal cu-zn alloy powder
Mass fraction account for 12%, the mass fraction of polypropylene glycol accounts for 15%；Again by membrane cutting growth 70mm, wide 46mm, with a thickness of 1 mm
Rectangle lamella；In the case where inert gas argon atmospher is enclosed, diaphragm is calcined to 1.5h at 560 DEG C and removes polypropylene glycol, then will be warm
Degree is increased to 1083 DEG C, is kept for 0.2 second, obtains graphite cathode piece.
By above-mentioned positive plate and negative electrode tab collocation commercialization electrolyte and commercialization diaphragm lamination assembling at lithium ion battery,
Test its energy density, multiplying power charging performance, multiplying power discharging property and cycle performance.
Comparative example 4:
By nickel-cobalt-manganternary ternary anode material collocation conductive black, PVDF binder and the solvent of model in the same manner as in Example 4
NMP is configured to nickel-cobalt-manganese ternary anode sizing agent, pours into slurry by infusion process in the foamed aluminium collector of 1mm thickness, then exists
It is dried at 120 DEG C, is cut into the positive plate of long 69mm, width 45mm.
By the graphite cathode material of model in the same manner as in Example 4 collocation conductive black, SBR binder, CMC stabilizer with
And aqueous solvent is configured to graphite cathode slurry, pours into slurry by infusion process in the foam copper current collector of 1mm thickness, then exists
It is dried at 100 DEG C, is cut into the negative electrode tab of long 70mm, width 46mm.
By above-mentioned positive plate and negative electrode tab arrange in pairs or groups model in the same manner as in Example 4 commercialization electrolyte and commercialization diaphragm
Lamination assembling tests its energy density, multiplying power charging performance, multiplying power discharging property and cycle performance at lithium ion battery.
Table 1
From table 1, Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6 result it is found that using lithium battery pole slice of the invention, battery energy can be improved
Metric density, while guaranteeing it with good high rate performance and cycle performance.
The poor reason of traditional lithium battery pole piece performance: 1. traditional lithium battery pole slices are using carbon-based conductive agent as activity
Electron propagation ducts between material granule；2. traditional lithium battery pole slice is needed active material using high polymer binder
Grain is bonded together, and inert high polymer binder, which is covered on active material particle surface, will increase impedance；3. macromolecule bonds
Agent adhesive property in the long-term cyclic process of pole piece can be deteriorated, and eventually lead to active material particle and fall off from conductive network, lead
Cycle performance is caused to deteriorate, this deterioration is for the biggish active material of volume change such as silicon-based anode material in those cyclic processes
The performances such as material are especially apparent, and comparative example 1 is using traditional lithium battery pole slice.
Lithium battery pole slice of the present invention improves the principle of battery energy density, high rate performance and cycle performance:
1. lithium battery pole slice of the invention is using continuous metal skeleton as electron propagation ducts, electric conductivity is excellent；2. passing through
Active material particle is limited in skeleton structure by continuous metal skeleton, is not needed using inert high polymer binder, therefore
It will not carry out additional impedance to electrode band to increase；3. continuous metal skeleton structure is made of metal material, metal material have compared with
High elasticity modulus can effective inhibitory activity material granule deformation, metal material plasticity with higher can be in activity
Material granule deformation therewith during deformation occurs guarantees that active material particle does not fall off from metal framework structure.Above 3
A factor collective effect determines that lithium battery pole slice of the invention can improve electricity by increasing pole piece thickness when designing battery
Pond energy density, while guaranteeing it with good high rate performance and cycle performance.
In addition, many reported in literature cross another technology, using porous metals (perforation copper foil, perforated aluminum foil, copper mesh,
Aluminium net etc.) or foam metal (foam copper, nickel foam, foamed aluminium etc.) as collector substitute the copper in current lithium ion battery
Foil and aluminum foil current collector, and it is prepared into pole piece, the high rate performance and cycle performance of battery can be improved to a certain extent.It needs
, it is noted that this technology is not significant to the promotion of performance, especially can not also be protected while being obviously improved energy density
Card improves the high rate performance and cycle performance of battery.Concrete reason is analyzed as follows:
1. usually being used and biography for porous metals (perforation copper foil, perforated aluminum foil, copper mesh, aluminium net, stainless (steel) wire etc.)
The similar method of system lithium ion battery, is made into slurry for active material, conductive agent and binder, is then coated on slurry porous
Metal collector surface is still unavoidable from carbon-based conductive agent poorly conductive in traditional collector, high polymer binder increases resistance
The three major issues that anti-, active material particle falls off, therefore can not fundamentally improve high rate performance and cycle performance, comparative example 2
Using such technical solution.
2. for foam metal (foam copper, nickel foam, foamed aluminium etc.), usually by active material, conductive agent and
Binder is made into slurry and slurry in the slurry, or by being pressurized then is poured into foam metal by foam metal dipping by force
Among gap, also have researcher remove conductive agent and binder and directly by active material particle pour into foam metal gap it
In.The problem of this technology, is that the gap of foam metal is usually irregular, and thickness is uneven, and having many bends or curves, because
This active material particle extraordinary can not fill among the gap with foam metal.If the partial size of active material particle is greater than
The hole of foam metal, then can not fill into；If the partial size of active material particle is less than the gap of foam metal, fill
Particle cannot keep and well contact with foam metal and (refer to the contact for having certain contact stress, it is therefore desirable to the work to particle
It is dynamic to have certain restriction effect)；The partial size of even active material particle is exactly equal to the aperture of foam metal, active material
The inlet that grain is stuck in hole also can prevent subsequent particle from going successively in hole, and prepare aperture and active material particle
The foam metal of exact matching is difficult.It is forthright again that the hole of foam metal and active material particle partial size mismatch will affect it
Energy and cycle performance, comparative example 3 and 4 is using such technical solution.
In lithium battery pole slice of the invention, metal material is directly contacted with active material particle surface；Metal material exists
Integrated continuous metal skeleton is formed after the fusion of active material particle surface, active material particle is limited in by metallic framework
In skeleton structure, the problem of active material particle falls off will not occur.Therefore, lithium battery pole slice of the invention fundamentally solves
Carbon-based conductive agent poorly conductive, high polymer binder increase impedance in traditional lithium battery pole slice, active material particle falls off
Three major issues.
Claims (9)
1. a kind of lithium battery pole slice, it is characterised in that: the lithium battery pole slice includes metallic framework (2) and active material (1), institute
Stating metallic framework (2) has open structure, and the active material (1) is embedded in the open structure of metallic framework (2), institute
State between metallic framework (2) and active material (1) that there are gap (3).
2. a kind of lithium battery pole slice according to claim 1, it is characterised in that: the active material (1) is positive-active
Substance or negative electrode active material.
3. a kind of lithium battery pole slice according to claim 1, it is characterised in that: the positive active material be cobalt acid lithium,
Lithium nickelate, spinel lithium manganate, layered lithium manganate, nickel cobalt binary material, nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material, phosphorus
At least one of sour iron lithium, spinel nickel LiMn2O4, lithium-rich manganese base material, transition metal oxide, transition metal phosphate；
The negative electrode active material is that graphite, hard charcoal, soft charcoal, carbonaceous mesophase spherules, lithium titanate, nano-silicon negative electrode material, silicon-carbon are compound
At least one of negative electrode material, the sub- silicium cathode material of oxidation.
4. a kind of lithium battery pole slice according to claim 1, it is characterised in that: the lithium battery pole slice with a thickness of 0.05
~10 mm。
5. a kind of preparation method of lithium battery pole slice described in claim 1-4 any claim, which is characterized in that step is such as
Under:
Step 1: a certain amount of larger molecular organics are first dissolved in formation larger molecular organics solution among solvent, wherein greatly
The mass fraction of molecular organic is 0.1 ~ 99.9%；
Step 2: metal material, active material, larger molecular organics solution are stirred into slurry according to a certain percentage,
By slurry coating film forming, obtain after solvent volatilization with a thickness of the diaphragm of 0.05 ~ 10 mm, in the diaphragm, the metal material
Mass fraction be 5 ~ 60%, the mass fractions of larger molecular organics is 0.1 ~ 20%, and surplus is the mass fraction of active material；
Step 3: first by diaphragm, 0.5 ~ 4h of high-temperature calcination removes big point at 300 ~ 600 DEG C under inert gas or nitrogen protection
Sub- organic matter, then M ± 50 DEG C are raised the temperature to, it is kept for 0.1 ~ 6000 second for metallic material, is had after cooling solidification
There is the metallic framework (2) of open structure, be filled with active material (1) in the metallic framework (2), lithium battery pole slice is made,
Wherein M is the fusing point of metal material.
6. a kind of preparation method of lithium battery pole slice according to claim 5, it is characterised in that: described in step 2
Metal material is metal powder and/or metallic fiber, and the particle size range of the metal powder is 0.01 ~ 1 μm；The metallic fiber
Diameter range is 0.01 ~ 5 μm, and length range is 0.05 ~ 100 μm.
7. a kind of preparation method of lithium battery pole slice according to claim 5, it is characterised in that: described in step 2
Metal material is the combination of one or more of nickel, aluminium, copper, iron, manganese, cobalt, gold, silver, zirconium, zinc, tin, titanium, bismuth.
8. a kind of preparation method of lithium battery pole slice according to claim 5, it is characterised in that: described in step 1
Larger molecular organics are polyethylene glycol oxide (PEO), polyethylene glycol (PEG), polypropylene glycol, polyvinyl alcohol, polyacrylonitrile, gather inclined fluorine
Ethylene (PVDF), polyacrylate, sodium carboxymethylcellulose (CMC), polyvinylpyrrolidone (PVP), polystyrene, surface are living
At least one of property agent；The solvent be ethyl alcohol, methanol, propyl alcohol, acetonitrile, acetone, water, N-Methyl pyrrolidone (NMP), N,
At least one of dinethylformamide (DMF), n,N-dimethylacetamide (DMAc), toluene.
9. a kind of lithium battery containing lithium battery pole slice described in claim 1-4 any claim, it is characterised in that: described
Lithium battery includes diaphragm, electrolyte and the lithium battery pole slice.
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