CN105336916A - Lithium ion battery pole piece and preparation method thereof - Google Patents
Lithium ion battery pole piece and preparation method thereof Download PDFInfo
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- CN105336916A CN105336916A CN201410280401.7A CN201410280401A CN105336916A CN 105336916 A CN105336916 A CN 105336916A CN 201410280401 A CN201410280401 A CN 201410280401A CN 105336916 A CN105336916 A CN 105336916A
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Abstract
The invention discloses a lithium ion battery pole piece preparation method. The method comprises the following steps: 1) coating a slurry containing an active substance, a conductive agent and a binder on two surfaces of a current collector, drying the two surfaces of the current collector to obtain the pole pieces of film sheets distributed on two surfaces of the current collector, wherein a thickness of the film sheet is greater than or equal to 50 [mu]m; 2) employing a static spinning method for spinning a conductive agent-containing static spinning solution to obtain a first conductive fibrous layer distributed on the film sheets; and 3) striping the pole pieces, employing the static spinning method for spinning the conductive agent-containing static spinning solution to obtain a second conductive fibrous layer distributed on two surfaces of the membrane sheets; connecting the second conductive fibrous layer with the current collector, the membrane sheets and the first conductive fibrous layer to form a continuous conductive network. The pole piece obtained by the preparation method has the continuous conductive fiber network, a multidimensional electron transfer channel can be formed, internal resistance of a battery is obviously reduced, and the lithium ion battery by employing the pole piece has ideal energy density and electrochemistry performance.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly, the present invention relates to a kind of electrodes of lithium-ion batteries and preparation method thereof.
Background technology
Lithium ion battery has that voltage is high, specific energy is large, the discharge and recharge life-span is long and the advantage such as safety and environmental protection, is therefore widely used in each electronic product (as mobile phone, digital camera, notebook computer, electric tool), portable compact electric apparatus, electric automobile and energy-storage system.
Along with the development of science and technology, more and more higher to the requirement of performance of lithium ion battery, the especially energy density of lithium ion battery.Therefore, the energy density how improving lithium ion battery has become the focus that domestic and international lithium electrical travelling industry is competitively studied.
At present, the method improving lithium ion battery energy density has a lot, such as, reduce the thickness of lithium ion battery electrode piece collector, reduce the thickness of barrier film and adopt the silica-based anode that energy density is higher.Wherein, by lithium ion battery electrode piece thickness is improved, also be a kind of effective means improving lithium ion battery energy density, concrete principle is: being improved by electrode plates thickness can the number of plies of corresponding minimizing inside battery battery core, decrease the space occupancy of electrode current collecting body and barrier film, for active material provides more space.
But, the same with additive method, being applied in improve while energy density of thick electrode pole piece also can bring negative effect to the performance of battery: during lithium ion battery work, electrode provides electrical conductivity passage by electrode current collecting body and the conductive agent be distributed in pole piece.When electrode plates thickness increases, on the one hand because the distance increase of pole piece active material and collector makes the path of electric transmission elongated, conductive agent can be deteriorated in the uniformity of pole piece inner dispersion thereupon on the other hand, the electron conduction of electrode can be made to be deteriorated, polarization during electrode work increases, and causes that battery capacity cannot normally play, high rate performance is poor, low temperature analyses the series of problems such as lithium and Capacity fading.
Especially, when heavy-current discharge, the lithium concentration in electrolyte reduces near collector place gradually by away from collector, causes the generation of concentration polarization, more remarkable in thick pole piece system.Larger concentration polarization brings the non-uniform Distribution of electrochemical reaction speed, make pole piece inside (near collector) active material almost cannot participate in electrochemical reaction, capacity is caused normally to play, and pole piece outside (away from collector place) active material deep discharge, and then structural deterioration during initiation long circulating, aggravation capacity attenuation.
By regulating pole piece porosity distribution in a thickness direction effectively can improve electrolyte wettability in pole piece, improve the migration velocity of lithium ion, thus the high rate performance difference can improved because the increase of pole piece thickness causes and capacity play problem on the low side.Such as, application number is pole piece structure and manufacture method thereof disclosed in the Chinese invention patent application of CN200580027135.6 and CN201210191956.5, all the angles of prolonging porosity on thickness direction from raising pole piece, improve the wettability of electrolyte in pole piece, reduce concentration polarization phenomenon.But, the ability that electronics transmits at negative or positive electrode is very large on electrochemical reaction polarization impact, even if adopt the fibrous conductive agent such as VGCF, carbon nano-tube, owing to disperseing to be difficult to evenly, be delivered to pole piece from collector, particularly the surface of thick pole piece, the path of electron transmission is elongated, internal resistance is increased, is unfavorable for the performance of capacity, low temperature, high rate performance.
In view of this, the necessary problem providing a kind of electrodes of lithium-ion batteries to solve its electron conduction difference, effectively to reduce the internal resistance of cell, for lithium ion battery provides sound assurance to the development in high-energy-density direction.
Summary of the invention
The object of the invention is to: a kind of electrodes of lithium-ion batteries and preparation method thereof is provided, with and overcome existing electrodes of lithium-ion batteries poor electric conductivity and the large defect of internal resistance.
In order to realize foregoing invention object, the invention provides a kind of preparation method of electrodes of lithium-ion batteries, it comprises the following steps:
1) slurry containing active material, conductive agent and binding agent is coated on the two sides of collector, obtain collector two sides after drying and to distribute chaffy pole piece, diaphragm thickness is more than or equal to 50 μm;
2) adopt electrospinning process, the electrostatic spinning solution containing conductive agent is spun to the first conductive fiber layer be distributed on diaphragm; And
3) by pole piece cutting, method of electrostatic spinning is adopted the electrostatic spinning solution containing conductive agent to be spun to the second conductive fiber layer being distributed in pole piece both sides, second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, forms continuous print conductive network.
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, described step 1) form diaphragm and step 2) form the first conductive fiber and hocket, diaphragm and the first conductive fiber layer are alternately distributed, described second conductive fiber layer connects collector, Multilayer Film and multilayer first conductive fiber layer, forms continuous print conductive network.
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, and described electrostatic spinning solution contains conductive agent, polymeric binder and solvent, and wherein, conductive agent is one or more in conductive black, carbon fiber, Graphene, carbon nano-tube; Polymeric binder is one or several in Kynoar, polymethyl methacrylate, polyacrylonitrile, polyethylene glycol oxide, polyvinyl alcohol; Solvent is one or more in DMF, DMA solvent, acetone, oxolane, methyl alcohol, and in the first conductive fiber layer, the second conductive fiber layer, the weight content of conductive agent is 5% ~ 80%.
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, described electrostatic spinning solution carries out under being configured in stirring at room temperature condition, concrete configuration technique is: be dissolved in solvent by conductive agent and polymeric binder by weight 5% ~ 80%, be mixed with the electrostatic spinning solution that conductive agent weight content is 5% ~ 15%.
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, described step 2) and 3) in electrospinning conditions be: electrostatic spinning voltage 10 ~ 20 kilovolts, the distance of syringe needle and pole piece 10 ~ 15 centimetres, spinning solution flow velocity 0.5 ~ 10 ml/hour.
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, described step 1) in the thickness of diaphragm be 50 ~ 200 μm, the thickness of the first conductive fiber layer and the second conductive fiber is 0.1 ~ 2 μm.
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, described step 1) in, the weight ratio of active material, conductive agent and binding agent is (89-98): (1-6): (1-5).
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, by through step 1) and step 2) obtained pole piece is colded pressing, after itemize, then pole piece both sides electrostatic spinning is formed the second conductive fiber layer connecting collector, diaphragm and the first conductive fiber layer.
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, described pole piece is positive plate, described binding agent is one or more in Kynoar, polyimides, polyamide and polyaniline, and described solvent is one or more in 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), acetone and oxolane.
One as the preparation method of electrodes of lithium-ion batteries of the present invention is improved, and described pole piece is negative plate, and described bonding agent is one or more in Kynoar, polytetrafluoroethylene, Lithium polyacrylate and butadiene-styrene rubber.
In order to realize foregoing invention object, present invention also offers a kind of electrodes of lithium-ion batteries, it diaphragm comprising collector and be distributed in collector two sides, the diaphragm of described collector is distributed with the first conductive fiber layer, the both sides of described pole piece are distributed with the second conductive fiber layer, second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, forms continuous print conductive network.
One as electrodes of lithium-ion batteries of the present invention is improved, and described diaphragm and the first conductive fiber layer are that multilayer is alternately distributed, and described second conductive fiber layer connects collector, Multilayer Film and multilayer first conductive fiber layer, forms continuous print conductive network.
One as electrodes of lithium-ion batteries of the present invention is improved, and the thickness of described diaphragm is 50 ~ 200 μm, and the thickness of described first conductive fiber layer and the second conductive fiber layer is 0.1 ~ 2 μm.
One as electrodes of lithium-ion batteries of the present invention is improved, conductive agent conductive black, carbon fiber, Graphene, carbon nano-tube or its combination is contained in described first conductive fiber layer and the second conductive fiber layer, in first conductive fiber layer, the second conductive fiber layer, the weight content of conductive agent is 5% ~ 80%.
One as electrodes of lithium-ion batteries of the present invention is improved, and described electrodes of lithium-ion batteries is positive plate.
One as electrodes of lithium-ion batteries of the present invention is improved, and described electrodes of lithium-ion batteries is negative plate.
In addition, present invention also offers a kind of lithium ion battery, it comprises positive plate, negative plate, is interval in barrier film between positive/negative plate, and electrolyte, and wherein, described positive plate is aforementioned positive electrode sheet, and/or described negative plate is aforementioned negative plate.
Relative to prior art, electrodes of lithium-ion batteries of the present invention has following architectural feature and technique effect:
1) thickness of diaphragm is relatively little, and therefore its inner conductive agent can be uniformly distributed, and ensures the good electronic conductivity of diaphragm self;
2) diaphragm and the first conductive fiber layer are alternately distributed, and can ensure good electronic conductivity between diaphragm;
3) the second conductive fiber layer by diaphragm and the coated formation of the first conductive fiber layer the contiguous network structure from collector to conductive fiber layer, provide electron transmission path more efficiently.
Therefore, electrodes of lithium-ion batteries of the present invention can overcome thick electrode pole piece electrical conductance path length and conductive agent defect pockety in prior art, solves the problem of lithium ion battery thick electrode pole piece electron conduction difference.Adopt the lithium ion battery of electrodes of lithium-ion batteries of the present invention not only to have desirable energy density and chemical property, and capacity is brought into normal play, high rate performance and cyclical stability significantly improve, and analyses lithium phenomenon and significantly improves.
In addition, relative to the conductive agent directly using the linear material such as carbon nano-tube, carbon fiber as pole piece particularly thick pole piece, adopt electrospinning process pulverous conductive agent can be made tunica fibrosa, cost is more easy to control; Adopt method of electrostatic spinning formed conductive mesh network layers dispersion evenly, not easily there is agglomeration; Adopt electrospinning process, increase electron transmission passage, improve high rate performance and the cryogenic property of battery core, less demanding to equipment, without the need to large-scale redevelopment production line.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, electrodes of lithium-ion batteries of the present invention and preparation method thereof and its Advantageous Effects are described in detail, in accompanying drawing:
Fig. 1 is the structural representation of the pole piece adopting method for preparing lithium ion battery pole pieces of the present invention to obtain.
Fig. 2 be the embodiment of the present invention 1 to 6 lithium ion battery and comparative example 1 lithium ion battery after being completely charged to 4.2V, DC internal resistance (DCR) curve when 25 DEG C of degree of discharge are 0% ~ 100%.
Fig. 3 be the embodiment of the present invention 1 to 6 lithium ion battery and comparative example 1 lithium ion battery (4.2V) 25 DEG C time, charge to 4.2V with 0.5C, then be discharged to the curve of 3.0V with 0.1C, 0.2C, 0.5C, 1C, 1.5C, 2C respectively.
Embodiment
In order to make goal of the invention of the present invention, technical scheme and technique effect more clear, below in conjunction with drawings and Examples, the present invention is described in more detail.Should be understood that, each embodiment provided in this specification is only to explain the present invention, is not intended to limit the present invention, and the present invention is not limited to each embodiment provided in specification.
Embodiment 1
The preparation of positive plate
1) by LiCoO
2(cobalt acid lithium), Super-P (conductive carbon black), PVDF (Kynoar) add N by weight 95:2.0:3.0, mix and stir in dinethylformamide (NMP) and obtain having the anode sizing agent of certain fluidity, anode sizing agent be evenly coated in the two sides of 14 μm of thick metal aluminum foils and dry and make positive plate (1), its one side coating thickness is 90 μm.
2) with carbon nano-tube (the diameter 10nm that the method for electrostatic spinning will prepare in advance, long 20 μm)/Kynoar/DMAC solution-polymerized SBR is on the two sides of positive plate (1) and dry, make the positive plate (2) that surface distributed has the first conductive fiber layer, electrostatic spinning voltage 15 kilovolts, the distance of syringe needle and positive plate (1) 10 centimetres, the flow velocity of spinning solution 1 ml/hour, the thickness of the first conductive fiber layer is 200nm.Wherein, carry out under the stirring at room temperature condition that is configured in of spinning solution: conductive agent-carbon nano-tube and polymer polyvinylidene fluoride are dissolved in solvent DMAC by weight 30%, are mixed with the solution that weight fraction is 5%.
3) in the coated on both sides above-mentioned steps 1 of positive plate (2)) in containing LiCoO
2anode sizing agent and dry make positive plate (3), one side coating thickness is 90 μm.
4) through colding pressing, itemize, in the both sides of positive plate (3), the both sides that the Carbon Nanotube/Polymer configured/DMAC solution adopts the method for electrostatic spinning to be coated on positive plate (3) are formed the second conductive fiber layer again, make positive plate (4), second conductive fiber side connects collector, diaphragm and the first conductive fiber layer, and the thickness of every side second conductive fiber layer is 500nm.
5) positive pole ear that the aluminium flake thick with 0.1mm is made is connected on obtained positive plate on aluminium foil.
As shown in Figure 1, wherein, 10 is metal aluminum foil to the structure of positive plate, and thickness is 14 μm; 20 for containing LiCoO
2diaphragm, thickness is 90 μm; 30 is the first conductive fiber layer containing conductive carbon nanotube formed by electrospinning process, and thickness is 200nm; 40 is the second conductive fiber layer containing conductive carbon nanotube formed by electrospinning process, and be attached to the both sides of positive plate, thickness is 500nm.
The preparation of negative plate
1) graphite, Super-P (conductive carbon black), SBR (StyreneButadieneRubber; butadiene-styrene rubber), CMC (water based adhesive; carboxymethyl cellulose) be added to the water mixing by weight 95.5:1.5:1.5:1.5 and stir and obtain having the cathode size of certain fluidity; above-mentioned cathode size be evenly coated in the two sides of 9 μm of thick metal copper foils and dry and make negative plate (1), its one side coating thickness is 100 μm.
2) with electrospinning process, the solution-polymerized SBR containing carbon nano-tube prepared in advance is also dried the negative plate (2) making surface distributed first conductive fiber layer on the two sides of negative plate (1), the thickness in monolayer of the first conductive fiber layer is 200nm, and the solution adopted when solution and spinning condition are prepared with positive plate is identical with spinning condition.
3) in the coated on both sides above-mentioned steps 1 of negative plate (2)) in containing graphite cathode size and dry make negative plate (3), one side coating thickness is 100 μm.
4) through colding pressing, itemize, in the both sides of negative plate (3), the both sides that the solution containing carbon nano-tube configured adopts the method for electrostatic spinning to be coated on negative plate (3) are formed the second conductive fiber layer again, make negative plate (4), second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, and the thickness of every side second conductive fiber layer is 500nm.
5) negative lug that the nickel sheet thick with 0.1mm is made is connected on after on Copper Foil, obtained negative plate, wherein, the structure of negative plate and the similar of positive plate.
The preparation of lithium ion battery
The positive plate made, negative plate and barrier film are made naked battery core by the mode of lamination or winding, and barrier film adopts polypropylene (PP)-polyethylene (PE)-polypropylene PP tri-layers laminated film; Battery core is loaded in battery packages shell, and inject electrolyte (with lithium hexafluoro phosphate (LiPF
6) be lithium salts, with the ethylene carbonate of 20%, the methyl ethyl carbonate of 30% and the dimethyl carbonate of 50% are solvent); Lithium ion battery is obtained with ageing process through changing into.
Embodiment 2
The preparation of positive plate
1) by LiCoO
2(cobalt acid lithium), Super-P (conductive carbon black), PVDF (Kynoar) add N by weight 95:2.0:3.0, mix and stir in dinethylformamide (NMP) and obtain having the anode sizing agent of certain fluidity, anode sizing agent be coated in the two sides of 14 μm of thick metal aluminum foils and dry and make positive plate (1), its one side thickness is 90 μm.
2) with carbon nano-tube (the diameter 10nm that the method for electrostatic spinning will prepare in advance, long 20 μm)/Kynoar/DMAC solution-polymerized SBR is on the two sides of positive plate (1) and dry, make the positive plate (2) that surface distributed has the first conductive fiber layer, electrostatic spinning voltage 15 kilovolts, the distance of syringe needle and pole piece (1) 10 centimetres, the flow velocity of spinning solution 1 ml/hour, the thickness of the first conductive fiber layer is 500nm.Wherein, carry out under the stirring at room temperature condition that is configured in of spinning solution: conductive agent-carbon nano-tube and polymer polyvinylidene fluoride are dissolved in solvent DMAC by weight 30%, are mixed with the solution that weight fraction is 5%.
3) in the coated on both sides above-mentioned steps 1 of positive plate (2)) in containing LiCoO
2anode sizing agent and dry make positive plate (3), one side coating thickness is 90 μm.
4) through colding pressing, itemize, in the both sides of positive plate (3), the both sides that the Carbon Nanotube/Polymer configured/DMAC solution adopts the method for electrostatic spinning to be coated on positive plate (3) are formed the second conductive fiber layer again, make pole piece (4), second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, and the thickness of every side second conductive fiber layer is 500nm.
5) positive pole ear that the aluminium flake thick with 0.1mm is made is connected on obtained positive plate on aluminium foil.
The preparation of negative plate
1) graphite, Super-P (conductive carbon black), SBR (StyreneButadieneRubber; butadiene-styrene rubber), CMC (water based adhesive; carboxymethyl cellulose) be added to the water mixing by weight 95.5:1.5:1.5:1.5 and stir and obtain having the cathode size of certain fluidity; above-mentioned cathode size be evenly coated in the two sides of 9 μm of thick metal copper foils and dry and make negative plate (1), its one side coating thickness is 100 μm.
2) with electrospinning process, the solution-polymerized SBR containing carbon nano-tube prepared in advance is also dried the negative plate (2) making surface distributed first conductive fiber layer on the two sides of negative plate (1), the thickness in monolayer of the first conductive fiber layer is 500nm, and the solution adopted when solution and spinning condition are prepared with positive plate is identical with spinning condition.
3) in the coated on both sides above-mentioned steps 1 of negative plate (2)) in containing graphite cathode size and dry make negative plate (3), one side coating thickness is 100 μm.
4) through colding pressing, itemize, in the both sides of negative plate (3), the both sides that the solution containing carbon nano-tube configured adopts the method for electrostatic spinning to be coated on negative plate (3) are formed the second conductive fiber layer again, make negative plate (4), second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, and the thickness of every side second conductive fiber layer is 500nm.
5) negative lug that the nickel sheet thick with 0.1mm is made is connected on after on Copper Foil, obtained negative plate.The preparation of lithium ion battery
The positive plate made, negative plate and barrier film are made naked battery core by the mode of lamination or winding, and barrier film adopts polypropylene (PP)-polyethylene (PE)-polypropylene PP tri-layers laminated film; Battery core is loaded in battery packages shell, and inject electrolyte (with lithium hexafluoro phosphate (LiPF
6) be lithium salts, with the ethylene carbonate of 20%, the methyl ethyl carbonate of 30% and the dimethyl carbonate of 50% are solvent); Lithium ion battery is obtained with ageing process through changing into.
Embodiment 3
The preparation of positive plate
1) by LiCoO
2(cobalt acid lithium), Super-P (conductive carbon black), PVDF (Kynoar) add N by weight 95:2.0:3.0, mix and stir in dinethylformamide (NMP) and obtain having the anode sizing agent of certain fluidity, anode sizing agent be evenly coated in the two sides of 14 μm of thick metal aluminum foils and dry and make positive plate (1), its one side coating thickness is 90 μm.
2) with carbon nano-tube (the diameter 10nm that the method for electrostatic spinning will prepare in advance, long 20 μm)/Kynoar/DMAC solution-polymerized SBR is on the two sides of positive plate (1) and dry, make the positive plate (2) that surface distributed has the first conductive fiber layer, electrostatic spinning voltage 15 kilovolts, the distance of syringe needle and positive plate (1) 10 centimetres, the flow velocity of spinning solution 1 ml/hour, the thickness of the first conductive fiber layer is 1000nm.Wherein, carry out under the stirring at room temperature condition that is configured in of spinning solution: conductive agent-carbon nano-tube and polymer polyvinylidene fluoride are dissolved in solvent DMAC by weight 30%, are mixed with the solution that weight fraction is 5%.
3) in the coated on both sides above-mentioned steps 1 of positive plate (2)) in containing LiCoO
2anode sizing agent and dry make positive plate (3), one side coating thickness is 90 μm.
4) through colding pressing, itemize, in the both sides of positive plate (3), the both sides that the Carbon Nanotube/Polymer configured/DMAC solution adopts the method for electrostatic spinning to be coated on positive plate (3) are formed the second conductive fiber layer again, make positive plate (4), second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, and the thickness of every side second conductive fiber layer is 500nm.
5) positive pole ear that the aluminium flake thick with 0.1mm is made is connected on obtained positive plate on aluminium foil.
The preparation of negative plate
1) graphite, Super-P (conductive carbon black), SBR (StyreneButadieneRubber; butadiene-styrene rubber), CMC (water based adhesive; carboxymethyl cellulose) be added to the water mixing by weight 95.5:1.5:1.5:1.5 and stir and obtain having the cathode size of certain fluidity; above-mentioned cathode size be evenly coated in the two sides of 9 μm of thick metal copper foils and dry and make negative plate (1), its one side coating thickness is 100 μm.
2) with electrospinning process, the solution-polymerized SBR containing carbon nano-tube prepared in advance is also dried the negative plate (2) making surface distributed first conductive fiber layer on the two sides of negative plate (1), the thickness in monolayer of the first conductive fiber layer is 1000nm, and the solution adopted when solution and spinning condition are prepared with positive plate is identical with spinning condition.
3) in the coated on both sides above-mentioned steps 1 of negative plate (2)) in containing graphite cathode size and dry make negative plate (3), one side coating thickness is 100 μm.
4) through colding pressing, itemize, in the both sides of negative plate (3), the both sides that the solution containing carbon nano-tube configured adopts the method for electrostatic spinning to be coated on negative plate (3) are formed the second conductive fiber layer again, make negative plate (4), second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, and the thickness of every side second conductive fiber layer is 500nm.
5) negative lug that the nickel sheet thick with 0.1mm is made is connected on after on Copper Foil, obtained negative plate.The preparation of lithium ion battery
The positive plate made, negative plate and barrier film are made naked battery core by the mode of lamination or winding, and barrier film adopts polypropylene (PP)-polyethylene (PE)-polypropylene PP tri-layers laminated film; Battery core is loaded in battery packages shell, and inject electrolyte (with lithium hexafluoro phosphate (LiPF
6) be lithium salts, with the ethylene carbonate of 20%, the methyl ethyl carbonate of 30% and the dimethyl carbonate of 50% are solvent); Lithium ion battery is obtained with ageing process through changing into.
Embodiment 4
The preparation of positive plate
1) by LiCoO
2(cobalt acid lithium), Super-P (conductive carbon black), PVDF (Kynoar) add N by weight 95:2.0:3.0, mix and stir in dinethylformamide (NMP) and obtain having the anode sizing agent of certain fluidity, anode sizing agent be evenly coated in the two sides of 14 μm of thick metal aluminum foils and dry and make positive plate (1), its one side coating thickness is 60 μm.
2) with carbon nano-tube (the diameter 10nm that the method for electrostatic spinning will prepare in advance, long 20 μm)/Kynoar/DMAC solution-polymerized SBR is on the two sides of positive plate (1) and dry, make the positive plate (2) that surface distributed has the first conductive fiber layer, electrostatic spinning voltage 15 kilovolts, the distance of syringe needle and positive plate (1) 10 centimetres, the flow velocity of spinning solution 1 ml/hour, the thickness of the first conductive fiber layer is 500nm.Wherein, carry out under the stirring at room temperature condition that is configured in of spinning solution: conductive agent-carbon nano-tube and polymer polyvinylidene fluoride are dissolved in solvent DMAC by weight 30%, are mixed with the solution that weight fraction is 5%.
3) in the coated on both sides above-mentioned steps 1 of positive plate (2)) in containing LiCoO
2anode sizing agent and dry make positive plate (3), one side coating thickness is 90 μm.
4) in the two sides of positive plate (3) the first conductive fiber layer that electrostatic spinning 500nm is thick again, positive plate (4) is obtained.
5) in the coated on both sides above-mentioned steps 1 of positive plate (4)) in containing LiCoO
2anode sizing agent and dry make positive plate (5), one side coating thickness is 60 μm.
6) through colding pressing, itemize, in the both sides of positive plate (5), the both sides that the Carbon Nanotube/Polymer configured/DMAC solution adopts the method for electrostatic spinning to be coated on positive plate (5) are formed the second conductive fiber layer again, make positive plate (6), second conductive fiber layer connects collector, Multilayer Film and multilayer first conductive fiber layer, and the thickness of every side second conductive fiber layer is 500nm.
7) positive pole ear that the aluminium flake thick with 0.1mm is made is connected on obtained positive plate on aluminium foil.
The preparation of negative plate
1) graphite, Super-P (conductive carbon black), SBR (StyreneButadieneRubber; butadiene-styrene rubber), CMC (water based adhesive; carboxymethyl cellulose) be added to the water mixing by weight 95.5:1.5:1.5:1.5 and stir and obtain having the cathode size of certain fluidity; above-mentioned cathode size be evenly coated in the two sides of 9 μm of thick metal copper foils and dry and make negative plate (1), its one side coating thickness is 70 μm.
2) with electrospinning process, the solution-polymerized SBR containing carbon nano-tube prepared in advance is also dried the negative plate (2) making surface distributed first conductive fiber layer on the two sides of negative plate (1), the thickness in monolayer of the first conductive fiber layer is 500nm, and the solution adopted when solution and spinning condition are prepared with positive plate is identical with spinning condition.
3) in the coated on both sides above-mentioned steps 1 of negative plate (2)) in containing graphite cathode size and dry make negative plate (3), one side coating thickness is 70 μm.
4) adopt the method for electrostatic spinning respectively in first conductive fiber layer of the two sides of negative plate (3) attachment 500nm, obtained negative plate (4).
5) in the dual coating above-mentioned steps 1 of negative plate (4)) in containing graphite cathode size and dry make negative plate (5), one side coating thickness is 60 μm.
6) through colding pressing, itemize, in the both sides of negative plate (5), the both sides that the solution containing carbon nano-tube configured adopts the method for electrostatic spinning to be coated on negative plate (5) are formed the second conductive fiber layer again, make negative plate (6), second conductive fiber layer connects collector, Multilayer Film and multilayer first conductive fiber layer, and the thickness of every side second conductive fiber layer is 500nm.
7) negative lug that the nickel sheet thick with 0.1mm is made is connected on after on Copper Foil, obtained negative plate.The preparation of lithium ion battery
The positive plate made, negative plate and barrier film are made naked battery core by the mode of lamination or winding, and barrier film adopts polypropylene (PP)-polyethylene (PE)-polypropylene PP tri-layers laminated film; Battery core is loaded in battery packages shell, and inject electrolyte (with lithium hexafluoro phosphate (LiPF
6) be lithium salts, with the ethylene carbonate of 20%, the methyl ethyl carbonate of 30% and the dimethyl carbonate of 50% are solvent); Lithium ion battery is obtained with ageing process through changing into.
Embodiment 5
Embodiment 5 is only with the difference of embodiment 1: replace carbon nano-tube with carbon black, and the concentration of electrostatic spinning solution is 50%, all the other are with embodiment 1.
Embodiment 6
Embodiment 6 is only with the difference of embodiment 1: replace carbon nano-tube with gas-phase growth of carbon fibre (VGCF), all the other are with embodiment 1.
Comparative example 1
Positive plate adopts the positive plate (1) in embodiment 1, and its one side coating thickness is 200 μm; Negative plate adopts the negative plate (1) in embodiment 1, its one side coating thickness 180 μm; The preparation of positive plate (1), negative plate (1) and lithium ion battery is substantially the same manner as Example 1.
Performance evaluation
Embodiment 1 to 6 lithium ion battery and comparative example 1 lithium ion battery are placed in insulating box, constant temperature 10 ± 2 DEG C, with 0.3C constant current charge to 4.2 ± 0.01V, then constant voltage charge, charge cutoff electric current is 0.05C, shelves 5 minutes, is then discharged to 3.0V with 0.5C, iterative cycles like this 10 times, then with constant voltage charge after 0.5C constant current to 4.2 ± 0.01V to 0.05C.
Lithium ion battery is taken apart in drying shed, find that embodiment 1 to 6 lithium ion battery all occurs without analysing lithium, and the negative terminal surface of comparative example 1 lithium ion battery all has the lithium metal of grey, as can be seen here, the low temperature that the negative plate adopting the inventive method to prepare can improve battery effectively analyses lithium situation; Adopt the conductive network of interval conductive fiber layer and outer conductive fibrage composition, effectively can improve the uniformity of pole piece internal current density, reduce electrochemical reaction polarization, improve and analyse lithium.
By embodiment 1 to 6 lithium ion battery and comparative example 1 lithium ion battery, probe temperature is 25 ± 2 DEG C, and rate of charge all with 0.5C constant current charge to 4.2 ± 0.01V, then uses constant voltage charge, and cut-off current is 0.05C; Leave standstill 30 minutes, then discharge 10 seconds with 0.1C, 1C discharges 1 second, and leave standstill 30 minutes, then discharge 6 minutes with 0.5C, so circulate, ending discharge voltage, to 3.0V, calculates the DC internal resistance of battery during different degree of discharge, as shown in Figure 2.
As can be seen from Figure 2, adopt the electrode system that traditional pole piece preparation technology prepares, its DC internal resistance is larger; And adopting the electrode system of conductive fiber layer network configuration, its DC internal resistance reduces.In addition, it can also be seen that from Fig. 2, the DC internal resistance of battery system not only increases along with the thickness increase of conductive fiber layer, also increase along with the increase of the conductive fiber number of plies, show: inner at pole piece, the distribution of electric current is more even, and pole piece all has the boundary layer of the close current potential with collector at different-thickness, the electron transmission impedance of pole piece inside can be greatly reduced, thus reduce internal resistance.
Comparatively speaking, adopt conductive fiber layer network prepared by the agent of the linear conductance such as carbon nano-tube and vapor-grown carbon fibers, relative to conductive carbon powder--the conductive fiber layer network that carbon black prepares, DC internal resistance is slightly low, illustrates that linear conductance agent has certain advantage in electron transmission ability.
By embodiment 1 to 6 lithium ion battery and comparative example 1 lithium ion battery, probe temperature is 25 ± 2 DEG C, and rate of charge all with 0.5C constant current charge to 4.2 ± 0.01V, then uses constant voltage charge, and cut-off current is 0.05C; Shelve 5 minutes, then respectively with multiplying power dischargings such as 0.1C, 0.2C, 0.5C, 1C, 1.5C, 2C, cut-ff voltage is 3.0V, and record the capability retention of battery under different discharge-rate, acquired results as shown in Figure 3.
As can be seen from Figure 3, when discharging under larger multiplying power condition, adopt the battery of conductive fiber layer network configuration, discharge-rate performance is highly improved, consistent with the result of battery DC inner walkway, the introducing of conductive fiber layer network, reduces the internal resistance of battery, improves the performance of battery charging and discharging.
In sum, by introducing one or more layers the first conductive fiber layer in negative plate and positive plate, and carry out the second conductive fiber layer in side coated, effectively can improve the ability that pole piece internal electron transmits, reduce the internal resistance of cell, significantly improve high rate performance, significantly improve low temperature and analyse lithium phenomenon.
It should be noted that, according to the above description the announcement of book and instruction, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention equivalent modifications more of the present invention and change.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (15)
1. a preparation method for electrodes of lithium-ion batteries, is characterized in that, comprises the following steps:
1) slurry containing active material, conductive agent and binding agent is coated on the two sides of collector, obtain collector two sides after drying and to distribute chaffy pole piece, diaphragm thickness is more than or equal to 50 μm;
2) adopt electrospinning process, the electrostatic spinning solution containing conductive agent is spun to the first conductive fiber layer be distributed on diaphragm; And
3) by pole piece cutting, method of electrostatic spinning is adopted the electrostatic spinning solution containing conductive agent to be spun to the second conductive fiber layer being distributed in pole piece both sides, second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, forms continuous print conductive network.
2. the preparation method of electrodes of lithium-ion batteries according to claim 1, it is characterized in that, described step 1) form diaphragm and step 2) form the first conductive fiber and hocket, diaphragm and the first conductive fiber layer are alternately distributed, described second conductive fiber layer connects collector, Multilayer Film and multilayer first conductive fiber layer, forms continuous print conductive network.
3. the preparation method of electrodes of lithium-ion batteries according to claim 1, it is characterized in that, described electrostatic spinning solution contains conductive agent, polymeric binder and solvent, and wherein, conductive agent is one or more in conductive black, carbon fiber, Graphene, carbon nano-tube; Polymeric binder is one or several in Kynoar, polymethyl methacrylate, polyacrylonitrile, polyethylene glycol oxide, polyvinyl alcohol; Solvent is one or more in DMF, DMA solvent, acetone, oxolane, methyl alcohol, and in the first conductive fiber layer, the second conductive fiber layer, the weight content of conductive agent is 5% ~ 80%.
4. the preparation method of electrodes of lithium-ion batteries according to claim 3, it is characterized in that, described electrostatic spinning solution carries out under being configured in stirring at room temperature condition, concrete configuration technique is: be dissolved in solvent by conductive agent and polymeric binder by weight 5% ~ 80%, be mixed with the electrostatic spinning solution that conductive agent weight content is 5% ~ 15%.
5. the preparation method of electrodes of lithium-ion batteries according to claim 1, it is characterized in that, described step 2) and 3) in electrospinning conditions be: electrostatic spinning voltage 10 ~ 20 kilovolts, the distance of syringe needle and pole piece 10 ~ 15 centimetres, spinning solution flow velocity 0.5 ~ 10 ml/hour.
6. the preparation method of electrodes of lithium-ion batteries according to claim 1, is characterized in that, described step 1) in the thickness of diaphragm be 50 ~ 200 μm, the thickness of the first conductive fiber layer, the second conductive fiber is 0.1 ~ 2 μm.
7. the preparation method of electrodes of lithium-ion batteries according to claim 1, it is characterized in that, by through step 1) and step 2) obtained pole piece is colded pressing, after itemize, then pole piece both sides electrostatic spinning is formed the second conductive fiber layer connecting collector, diaphragm and the first conductive fiber layer.
8. the preparation method of electrodes of lithium-ion batteries according to claim 1, it is characterized in that, described pole piece is positive plate, described binding agent is one or more in Kynoar, polyimides, polyamide and polyaniline, and described solvent is one or more in 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethyl formamide, dimethyl sulfoxide (DMSO), acetone and oxolane.
9. the preparation method of electrodes of lithium-ion batteries according to claim 1, is characterized in that, described pole piece is negative plate, and described bonding agent is one or more in Kynoar, polytetrafluoroethylene, Lithium polyacrylate and butadiene-styrene rubber.
10. an electrodes of lithium-ion batteries, it diaphragm comprising collector and be distributed in collector two sides, it is characterized in that: the diaphragm of described collector is distributed with the first conductive fiber layer, the both sides of described pole piece are distributed with the second conductive fiber layer, second conductive fiber layer connects collector, diaphragm and the first conductive fiber layer, forms continuous print conductive network.
11. electrodes of lithium-ion batteries according to claim 10, it is characterized in that, described diaphragm and the first conductive fiber layer are that multilayer is alternately distributed, and described second conductive fiber layer connects collector, Multilayer Film and multilayer first conductive fiber layer, forms continuous print conductive network.
12. electrodes of lithium-ion batteries according to claim 10, is characterized in that, the thickness of described diaphragm is 50 ~ 200 μm, and the thickness of described first conductive fiber layer and the second conductive fiber layer is 0.1 ~ 2 μm.
13. electrodes of lithium-ion batteries according to claim 10, it is characterized in that, conductive agent conductive black, carbon fiber, Graphene, carbon nano-tube or its combination is contained in described first conductive fiber layer and the second conductive fiber layer, in first conductive fiber layer, the second conductive fiber layer, the weight content of conductive agent is 5% ~ 80%.
14., according to claim 10 to the electrodes of lithium-ion batteries according to any one of 13, is characterized in that, described electrodes of lithium-ion batteries is positive plate or negative plate.
15. 1 kinds of lithium ion batteries, it comprises positive plate, negative plate, is interval in barrier film between positive/negative plate, and electrolyte, it is characterized in that: described positive plate is positive plate according to claim 14, and/or described negative plate is negative plate according to claim 14.
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| CN107978732B (en) | 2020-03-27 |
| CN107978732A (en) | 2018-05-01 |
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