CN101174685A - Anode or cathode pole piece of lithium ion battery and coating method thereof - Google Patents
Anode or cathode pole piece of lithium ion battery and coating method thereof Download PDFInfo
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- CN101174685A CN101174685A CNA2007100359705A CN200710035970A CN101174685A CN 101174685 A CN101174685 A CN 101174685A CN A2007100359705 A CNA2007100359705 A CN A2007100359705A CN 200710035970 A CN200710035970 A CN 200710035970A CN 101174685 A CN101174685 A CN 101174685A
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Abstract
The present invention relates to a lithium-ion battery anode or cathode pole piece and a spreading method of the anode pole piece or the cathode pole piece, wherein, the anode pole piece and the cathode pole piece consists of a foil, a conducting adhesive thin layer and an electrode active material layer in turn; the thickness of the conducting adhesive thin layer is five to ten microns. The electrode pole piece is made in the procedures that a layer of conducting adhesive thin layer in the thickness of five to ten microns are pre-coated on the surface of the foil before the sizing agent is spread, so that a conducting adhesive thin layer having good adhesive force, good conductivity and compact structure is formed on the surface of the foil. Then the electrode active material sizing agent is spread on the conducting adhesive thin layer, and is dried under an appropriate temperature to produce a required pole piece. The present invention can reduce the surface of the foil, and can improve the wetting quality of the sizing agent, thereby improving the adhesion performance of the anode material and the collecting body (aluminum foil) so as to reduce the powder-dropping of the battery during the cycling process, and to prolong the cycling service life of the battery; moreover, the present invention can reduce the content of the adhesive agent in the sizing agent, and improve the utilization rate of the active substance, and the method of the present invention does not produce negative influence on the performance of the battery.
Description
Technical field
The present invention relates to a kind of lithium ion cell positive or cathode pole piece and coating process thereof.
Background technology
Lithium ion battery is the green high-capacity rechargeable battery of latest generation, succeed in developing by Japanese Sony Corporation first in nineteen ninety, along with continuous progress in science and technology, the energy density and the capacity of lithium ion battery constantly increase, lithium ion battery replaces nickel-cadmium cell and Ni-MH battery gradually with its superior performance, become the first-selected rechargeable battery of portable electric appts, have broad application prospects in all many-sides such as video camera, digital camera, mobile phone and notebook computer, electric automobile, space technology, national defense industry.
Though the lithium ion battery performance is more superior, but on manufacture craft, also there are some problems, the making and the performance of battery caused some harmful effects, as the easy dry linting of cell electrode piece, cause the capacity of battery low, cycle life is poor, internal resistance is big, the production cost of raw material is high.Now solving the most frequently used method of this type of problem is the consumption that increases or improve binding agent and conductive agent, the big increase of internal resistance of battery, specific capacity reduce, poor, the high influence of the production cost of raw material of cycle life but the consumption increase of binding agent can make, and the consumption of conductive agent has similar situation.Therefore, be in order to optimize the lithium ion battery performance, improve its market competitiveness, avoid in the process of slurry, adding a large amount of binding agents, and make it the phenomenon of dry linting in the process of coating and film-making, no longer occur, the content of electrode active material in slurry is increased, thereby the specific capacity of battery is increased.The present invention is directed to some technical defectives that the lithium ion battery plus-negative plate pole piece exists aspect coating, a kind of new coating process is provided.
Summary of the invention
The objective of the invention is to improve its market competitiveness in order to optimize the lithium ion battery performance, some the technical defectives according to the lithium ion battery plus-negative plate pole piece exists provide a kind of new lithium ion cell positive or cathode pole piece and coating process thereof.Make density is little in the electrode slurry, specific area is big material can be better and foil bond together, avoid the appearance dry linting phenomenon of battery in assembling and cyclic process, reduce the internal resistance of cell, improve the utilance of active material, improve battery performance.
Purpose of the present invention realizes by following manner.
A kind of lithium ion battery positive and negative electrode pole piece, described positive and negative electrode pole piece is made up of foil, conducting resinl thin layer, electrode active material layers successively, and the conducting resinl thickness of thin layer is 5～10 μ m.
The conducting resinl thin layer of described positive and negative plate comprises conductive agent, binding agent and solvent.
In the anode pole piece conducting resinl thin layer, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer at least; Binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least; Solvent is the N-methyl pyrrolidone.
In the described cathode pole piece conducting resinl thin layer, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer at least; Binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least; Solvent is a kind of in N-methyl pyrrolidone, the pure water; Adhesive comprises a kind of among polytetrafluoroethylene, polyvinylidene fluoride, CMC, the SBR at least.
Binding agent in the conducting resinl and solvent are pressed mass ratio 1: 8-12 and are mixed.
The coating process of described a kind of lithium ion battery positive and negative electrode pole piece,
1) preparation of conducting resinl thin layer joins binding agent and solvent in the agitated kettle, after high-speed stirred mixes, adds required conductive agent again, makes the conducting resinl emulsion after mixing; Conducting resinl is added in the feed chute, adjust the cutter table gap of coating machine, make through heater, to make the foil surface form the conducting resinl thin layer that one deck is firm with the foil bonding, rough surface is uneven by the glue-line that forms one deck 5～10 μ m on the foil surface;
2) coat the positive electrode active materials slurry coating of required surface density on conductive layer thin layer surface, required pole piece is made in oven dry then.
In the anode pole piece conducting resinl, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer at least; Binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least; Solvent is the N-methyl pyrrolidone.
In the described cathode pole piece conducting resinl, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer at least; Binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least; Solvent is a kind of in N-methyl pyrrolidone, the pure water; Adhesive comprises a kind of among polytetrafluoroethylene, polyvinylidene fluoride, CMC, the SBR at least.
Binding agent in the conducting resinl and solvent are pressed mass ratio 1: 8-12 and are mixed.
The preparation of described conducting resinl, preferably binding agent and solvent are joined in the agitated kettle in 1: 10 ratio of mass ratio, after high-speed stirred mixes, add required conductive agent (concrete ratio is decided on different materials) again, make the conducting resinl emulsion after mixing.
The present invention is a precoating layer conducting resinl before making coating sizing-agent, form the hard-packed conducting resinl thin layer that one deck has good cohesive force and conductivity on the foil surface, on this layer conducting resinl thin layer, carry out the coating of electrode active material slurry again, under suitable temperature, dry, and make required pole piece.
The method of the present invention by precoating layer conducting resinl on the foil surface make density is little in the electrode slurry, specific area is big material can be better and foil bond together, can reduce the surface energy of foil, improve the wettability of slurry, thereby improve the adhesive property of positive electrode and collector (aluminium foil), reduce the dry linting phenomenon of battery in cyclic process, make the cycle life of battery longer, but also the content that can reduce binding agent in the slurry improves the utilance of active material, and this kind method itself can not produce passive influence to the performance of battery.
One aspect of the present invention, under the situation that does not influence the slurry adhesive property, thereby relatively improve the specific capacity of the utilance raising battery of both positive and negative polarity active material by the conducting resinl thin layer that applies, reduce the dry linting phenomenon of battery in manufacturing process and in the cyclic process, improve the cycle performance of battery; On the other hand, relatively reduce the cost of raw material of battery, improve its market competitiveness.
The made pole piece of coating process of the lithium ion battery plus-negative plate pole piece that the present invention program provides is used in being also advantageous in that on the lithium ion battery:
A is coated with the foil rough surface injustice of conducting resinl thin layer and contains the strong binding agent of polarity, can significantly improve the cementitiousness of electrode active material and base material, improves every performance of pole piece, improves the operability of pole piece in rolling film, assembling process.
B can reduce the content of binding agent in the slurry and the content of conductive agent because the cohesive force in the conducting resinl thin layer strengthens, and increases the utilance of electrode active material, reduces the internal resistance of battery, relatively reduces the production cost of raw material of battery.
C reduces the dry linting phenomenon of battery in the process of coating and film-making and in cyclic process because cohesive force strengthens, and makes the cycle life of battery longer.
D can reduce the surface density of pole piece along with the raising of active material proportion under the certain situation of capacity, improve the performance of battery.
Description of drawings
Fig. 1 is the schematic flow sheet that reaches of apparatus for coating of the present invention.
1 unwinding device among Fig. 1,2 conducting resinl grooves, 3 heaters, 4 slurry tanks, 5 baking ovens, 6 wrap-ups.
Embodiment
The collector of the lithium ion battery negative that the present invention program provides is selected aluminium foil for use, anodal conducting resinl comprises conductive agent, binding agent and solvent, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer etc. at least, described binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least, and described solvent is the N-methyl pyrrolidone.Positive electrode material is formed and is comprised positive active material, conductive agent and binding agent.Wherein positive active material is selected for use and is comprised in cobalt acid lithium, LiMn2O4, LiFePO4, lithium manganese phosphate, cobalt phosphate lithium, lithium nickelate, lithium nickel cobalt dioxide, nickel LiMn2O4, the nickel manganese cobalt acid lithium one or more at least, conductive agent is selected for use and is comprised a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, acetylene black, conductive carbon black, stone etc. at least, and binding agent is selected for use and comprised a kind of among PTFE (polytetrafluoroethylene), the PVDF (polyvinylidene fluoride) at least.
The collector of the lithium ion battery negative that the present invention program provides is selected Copper Foil for use, conducting resin for negative pole comprises conductive agent, binding agent and solvent, described conductive agent comprises carbon nano-fiber at least, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone is deceived powder, a kind of in the conducting polymer etc., described binding agent comprises polytetrafluoroethylene at least, a kind of in the polyvinylidene fluoride, described solvent is the N-methyl pyrrolidone, a kind of in the pure water etc., described bonding mixture comprises polytetrafluoroethylene at least, polyvinylidene fluoride, SBR (butadiene-styrene latex), a kind of among the CMC (carboxymethyl cellulose) etc.Negative material is formed and is comprised material with carbon element, conductive agent and binding agent, wherein said material with carbon element comprises that at least artificial stone is black, natural stone is black, natural modified stone is black, carbon fiber, carbonaceous mesophase spherules, needle coke, tin oxide, lithium titanate, a kind of in the black powder of stone etc., conductive agent is selected for use and is comprised carbon nano-fiber at least, carbon nano-tube, nano-silver powder, acetylene black, conductive carbon black, a kind of in the black powder of stone etc., binding agent is selected for use and is comprised PTFE (polytetrafluoroethylene) at least, PVDF (polyvinylidene fluoride), SBR (butadiene-styrene latex), CMC (carboxymethyl cellulose), a kind of among the MC (methylcellulose) etc.
A kind of preparation of anode slice of lithium ion battery:
(1) accurately weighing 100 restrains PVDF, 100 gram conductive carbon blacks, 1000 gram NMP.
(2) preparation of conducting resinl at first, adds 1000 gram NMP in the de-airing mixer, slowly adds 100 gram PVDF again, stirs, and PVDF is dissolved fully, after mixing, adds 100 gram conductive carbon blacks again, mixes and promptly makes anodal conducting resinl emulsion.
(3) anode electrode material paste preparation: 94.5 gram cobalt acid lithiums, 3.0 gram conductive carbon blacks, 2.5 gram PVDF and 50 gram NMP mix and promptly are prepared into the anode electrode material paste.
(4) the conducting resinl emulsion that makes is put into the conducting resinl groove 2 of Fig. 1, on unwinding device 1, install aluminium foil (thick 0.018mm ± 0.002mm * wide 260mm ± 1.0mm), the anode electrode material paste is put into slurry tank 4, machine, adjust the conducting resinl thickness (5～10 μ m) of baking temperature (90～110 ℃), coating, (anodal coating single face surface density is 205 ± 5g/m to the anode electrode slurry surface density of coating
2, the two-sided surface density of anodal coating is 410 ± 10g/m
2), the conducting resinl emulsion is coated on the aluminium foil, forms the glue-line of one deck 5～10 μ m at aluminium foil surface, after heater 3 dryings, makes aluminium foil surface form the conductive layer thin layer that one deck is firm with the foil bonding, rough surface is uneven.Adjust the cutter table gap of coating machine, at the made slurry coating of coating required surface density on one deck conductive layer thin layer aluminium foil surface that is covered with, required anode pole piece is made in oven dry then.
A kind of preparation of lithium ion battery negative pole piece:
(1) accurately weighing 50 restrains CMC, 100 gram SBR emulsions, 100 gram conductive carbon blacks, 1000 gram pure water.
(2) preparation of conducting resinl at first, adds 1000 gram pure water in the de-airing mixer, slowly adds 50 gram CMC again, after stirring well, adds 100 gram SBR emulsions, after mixing, adds 100 gram conductive carbon blacks again, mixes and promptly makes the conducting resin for negative pole emulsion.
(3) negative electrode material slurry preparation: 95.4 gram Delaniums, 1 gram conductive carbon black, 1.6 gram CMC, 2 gram SBR and 100 gram pure water mix and promptly are prepared into the negative electrode material slurry.
(4) the conducting resinl emulsion that makes is put into the conducting resinl groove 2 of Fig. 1, on unwinding device 1, install Copper Foil (thick 0.012mm ± 0.002mm * wide 240mm ± 1.0mm), the negative electrode material slurry is put into slurry tank 4, machine, adjust the conducting resinl thickness (5～10 μ m) of baking temperature (90～110 ℃), coating, (negative pole coating single face surface density is 0.97 ± 0.02g/dm to the negative electrode slurry surface density of coating
2, it is 1.94 ± 0.02g/dm that negative pole is coated with two-sided surface density
2), the conducting resinl emulsion is coated on the aluminium foil, forms the glue-line of one deck 5～10 μ m at copper foil surface, after heater 3 dryings, makes copper foil surface form the conductive layer thin layer that one deck is firm with the foil bonding, rough surface is uneven.Adjust the cutter table gap of coating machine, at the made slurry coating of coating required surface density on one deck conductive layer thin layer copper foil surface that is covered with, required cathode pole piece is made in oven dry then.
Claims (9)
1. lithium ion cell positive or cathode pole piece, it is characterized in that: described negative or positive electrode pole piece is made up of foil, conducting resinl thin layer, electrode active material layers successively, and the conducting resinl thickness of thin layer is 5～10 μ m.
2. a kind of lithium ion cell positive according to claim 1 or negative pole utmost point pole piece is characterized in that: the conducting resinl thin layer of described negative or positive electrode pole piece comprises conductive agent, binding agent and solvent.
3. a kind of lithium ion cell positive according to claim 2 or cathode pole piece, it is characterized in that: in the anode pole piece conducting resinl thin layer, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer at least; Binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least; Solvent is the N-methyl pyrrolidone.
4. a kind of lithium ion cell positive according to claim 2 or negative pole utmost point pole piece, it is characterized in that: in the described cathode pole piece conducting resinl thin layer, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer at least; Binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least; Solvent is a kind of in N-methyl pyrrolidone, the pure water; Adhesive comprises a kind of among polytetrafluoroethylene, polyvinylidene fluoride, CMC, the SBR at least.
5. according to claim 2 or 3 or 4 described a kind of lithium ion cell positives or negative pole utmost point pole piece, it is characterized in that: binding agent in the conducting resinl and solvent are pressed mass ratio 1: 8-12 and are mixed.
6. the coating process of described a kind of lithium ion cell positive of claim 2 or negative pole utmost point pole piece is characterized in that:
1) preparation of conducting resinl thin layer joins binding agent and solvent in the agitated kettle, after high-speed stirred mixes, adds required conductive agent again, makes the conducting resinl emulsion after mixing; Conducting resinl is added in the feed chute, adjust the cutter table gap of coating machine, make through heater, to make the foil surface form the conducting resinl thin layer that one deck is firm with the foil bonding, rough surface is uneven by the glue-line that forms one deck 5～10 μ m on the foil surface;
2) coat the positive electrode active materials slurry coating of required surface density on conductive layer thin layer surface, required pole piece is made in oven dry then.
7. according to the coating process of described a kind of lithium ion cell positive of claim 6 or negative pole utmost point pole piece, it is characterized in that: in the anode pole piece conducting resinl, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer at least; Binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least; Solvent is the N-methyl pyrrolidone.
8. a kind of lithium ion cell positive according to claim 6 or cathode pole piece, it is characterized in that: in the described cathode pole piece conducting resinl, described conductive agent comprises a kind of in the black powder of carbon nano-fiber, carbon nano-tube, nano-silver powder, copper nanoparticle, nano-nickel powder, acetylene black, conductive carbon black, stone, the conducting polymer at least; Binding agent comprises a kind of in polytetrafluoroethylene, the polyvinylidene fluoride at least; Solvent is a kind of in N-methyl pyrrolidone, the pure water; Adhesive comprises a kind of among polytetrafluoroethylene, polyvinylidene fluoride, CMC, the SBR at least.
9. according to claim 6 or 7 or 8 described a kind of lithium ion cell positive or cathode pole pieces, it is characterized in that: binding agent in the conducting resinl and solvent are pressed mass ratio 1: 8-12 and are mixed.
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| CN114447337B (en) * | 2022-02-11 | 2023-09-01 | 湖北亿纬动力有限公司 | Conductive adhesive of negative electrode slurry, and preparation method and application thereof |
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