CN103326027A - Lithium ion battery cathode and lithium ion battery - Google Patents
Lithium ion battery cathode and lithium ion battery Download PDFInfo
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- CN103326027A CN103326027A CN2013102085620A CN201310208562A CN103326027A CN 103326027 A CN103326027 A CN 103326027A CN 2013102085620 A CN2013102085620 A CN 2013102085620A CN 201310208562 A CN201310208562 A CN 201310208562A CN 103326027 A CN103326027 A CN 103326027A
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Abstract
The invention discloses a lithium ion battery cathode. The lithium ion battery cathode comprises a cathode current collector and a cathode active-substance layer coated on the cathode current collector. The cathode active-substance layer comprises a cathode active-substance, a conductive agent, a polymer thickening agent, a water emulsion-type polymer binder and a water soluble polymer binder. The water soluble polymer binder is polyethyleneimine. A weight ratio of the water emulsion-type polymer binder to the water soluble polymer binder is in a range of (10: 90)-(90: 10). The lithium ion battery cathode can obviously improve the adhesion between the cathode active-substance layer and the cathode current collector and among particles in the cathode active-substance layer thereby improving structure stability of the cathode active-substance layer in long-term battery cycle and reducing a use amount of the polymer binders having electrochemical inertia, reducing a battery volume expansion ratio in cycle, and improving low temperature, multiplying power, cycle performances and energy density of a polymer lithium ion battery. The invention also discloses a lithium ion battery.
Description
Technical field
The invention belongs to technical field of lithium ion, relate in particular to a kind of lithium ion battery negative and lithium ion battery.
Background technology
Lithium ion battery is since commercialization is promoted, with its high-energy-density, high working voltage, have extended cycle life, memory-less effect, environmental protection and the large I of size shape according to the actual requirements the plurality of advantages such as flexible design be widely used as the power supply of various walkie electronic apparatus, the application that these are wide and various actual demand have greatly promoted the development of lithium ion battery.
High speed development along with the mobile electron electric equipment, requirement has higher capacity for the powerful equipment of these frivolous portable functions provides the lithium ion battery of power supply, needs thus exploitation than conventional lithium ion battery more high working voltage, more high-energy-density and more long-life battery.The lifting of these performances can realize by material and the manufacturing process that improvement relates to lithium ion battery.At present, a large amount of research work all concentrates on the critical materials such as positive pole, negative pole, barrier film and electrolyte with regard to the lithium ion battery material aspect.
Performance of lithium ion battery depends primarily on electrode, electrolyte and other auxiliary material.Especially, electrode property depends on electrode active material, collector and between electrode active material layers and the electrode current collecting body and the binding agent of cohesive force is provided between the electrode active material layer internal particle.
Binding agent is between negative active core-shell material, between negative active core-shell material and the conductive agent, the form by covalent bond or non-covalent bond (model ylid bloom action) between negative active core-shell material, conductive agent and metal collector provides bonding force and participates in constructing of negative electrode active material surface SEI film.Aspect negative pole, after between the negative electrode active material layers such as lithium insertion graphite, the volume of active material expands, along with periodically discharging and recharging, this circulative Swelling and contraction back and forth occurs, binding agent has played following two Main Functions in this periodic process: (1) binding agent provides strong bonding force in the cathode pole piece system, and electronics and lithium ion graceful migration in electrode guarantees that the internal resistance of electrode remains at low levels; (2) be buffered in the change in volume of the active material that produces in the charge and discharge process, even so that after expansion and contraction, also can keep original cohesive force and the electrode interior structure of binding agent.But the non-covalent bond that binding agent provides in the cathode pole piece system (model ylid bloom action) active force can reduce because polymeric binder under electrolyte soaks Swelling in various degree occurs, when pole piece thickness increases or selects the larger active material of dilatancy (silicon, silica etc.), can cause thus the loose of negative electrode active material layer and come off, and then embedding difficulty, polarization increase so that lithium ion takes off, analyse the serious problems such as lithium, high rate performance variation and cycle life reduction in the cyclic process.
Summary of the invention
The object of the invention is to: for the restriction of current material performance, and provide a kind of lithium ion battery negative and lithium ion battery, this lithium ion battery negative can significantly improve between negative electrode active material layer and the negative current collector and cohesive force between the negative electrode active material layer internal particle, improve the structural stability of negative electrode active material layer in the long-term cyclic process of battery, and the use amount of the polymeric binder of reduction electrochemistry inertia, suppress the cubical expansivity of battery in cyclic process, improve low temperature, multiplying power, cycle performance and the energy density of lithium ion battery.
In order to achieve the above object, the invention provides a kind of lithium ion battery negative, this technical scheme is as follows: a kind of lithium ion battery negative, comprise negative current collector and the negative electrode active material layer of coating described negative current collector, described negative electrode active material layer comprises negative electrode active material, conductive agent, polymer viscosifier, water milk type polymer binding agent and water-soluble polymeric binder, described water-soluble polymeric binder is polymine, and the weight rate of described water milk type polymer binding agent and described water-soluble polymeric binder is 10:90 ~ 90:10.
Although the chemical formula of polymine can with-［ CH2CH2NH ］-represent, the chemical constitution that contains one-level, secondary, three grades of side chains can be used too.Especially, on its molecular structure, Hi-fax imines, branched chain type polymine and hyperbranched type polymine all can be used among the present invention.The structure of commercially available polyethylene imines can be the structure with branching of epomine, is normally prepared by the acid catalysis ring-opening reaction of aziridine, and its polymer pole is soluble or be scattered in the water.Polymine can have 500～1,000,000 g/mol even higher molecular weight, but is applicable among the present invention, and preferred typical weight average molecular weight is 5,000～500,000 g/mol.Polymine can be protonated with acid, form around a kind of polyethyleneimine: amine salt in the medium, depend on the pH value and form a kind of can be partly or entirely from the product of separating, the pH value that is applicable to the aqueous solution of polymine 5% concentration of the present invention should be in 9～12 scope.
Described water-soluble polymeric binder-polymine, owing to having a large amount of polar groups on its molecular structure, comprise primary amino radical, secondary amino group and uncle are amino, these polar groups can and the negative current collector Copper Foil between form coordinate bond, with negative electrode active material and the lip-deep polar group (carboxyl of conductive agent, hydroxyl) forms chemical bond or the stronger intermolecular force-Van der Waals force (induction force of generation, dispersion force, hydrogen bond force), thereby providing stronger bonding force between negative electrode active material layer and the negative current collector and between the negative electrode active material layer internal particle, and the bonding force that forms thus is not easy to be damaged and affects bond effect under the effect of electrolyte.The polar group that these electron donations are very strong in addition help to increase lithium salts dissociation and with lithium cation generation complexing, and polymine has lower glass transition temperature, its molecule segment has enough compliances, can help to improve lithium ion in the conduction of electrode interior.
Described water milk type polymer binding agent is at least a in butadiene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, chloroprene rubber, ethylene propylene diene rubber and the acrylic rubber, but is not limited to this.Described water milk type polymer binding agent can be anyly well-knownly in the prior art to have a viscoelastic binding agent.
The percentage by weight that described water milk type polymer binding agent accounts for described negative electrode active material layer total weight is 0.5～10 %.
The percentage by weight that described water milk type polymer binding agent accounts for described negative electrode active material layer total weight is 0.5～3 %.
Described polymine is the homopolymers of aziridine, aziridine mixture or the copolymer of aziridine mixture, and the macromolecular structure of described polymine comprises line style, branched chain type and hyperbranched type.
The percentage by weight that described polymine accounts for described negative electrode active material layer total weight is 0.5～10 %.
The percentage by weight that described polymine accounts for described negative electrode active material layer total weight is 0.5～3 %.
In the formula of size, if the consumption of binding agent is very few, can cause the bonding variation of negative electrode active material layer and collector, negative electrode active material layer easily comes off in pole piece and the battery manufacturing process.In addition, also can cause the structural stability variation of negative electrode active material layer in the long-term cyclic process of battery, reduce and the demoulding that causes etc. such as the caking property of cubical expansivity increase, negative electrode active material layer and the negative current collector of negative electrode active material layer in cyclic process, these problems can have a strong impact on the cycle life of battery.Otherwise if the consumption of binding agent too much (mass fraction is greater than 10%), binding agent then may coat the active material surface, causes impedance to increase, and affects battery performance.
The weight average molecular weight of described polymine is 500～1,000,000 g/mol.
The weight average molecular weight of described polymine is 5,000～500,000 g/mol.
Comprise in the large molecule of described polymine that primary amino radical, secondary amino group and uncle are amino, with respect to amino total amount, the molar ratio of primary amino radical is more than 20%, and the molar ratio of secondary amino group is more than 20%, and the molar ratio of uncle's amino is in 60%.
The pH value of the aqueous solution of described polymine 5% concentration is 9～12.
Described negative electrode active material is at least a in native graphite, Delanium, graphitized carbon fibre, graphitized intermediate-phase carbon microballon, amorphous carbon, silicon, silica, tin oxide and the ashbury metal compound.
Described conductive agent is at least a in conductive black, carbon fiber, carbon nano-tube and the Graphene.
Described polymer viscosifier is at least a in sodium carboxymethylcellulose, CMC, hydroxyethylcellulose, polyacrylic acid and the polyvinyl alcohol.
The percentage by weight that described negative electrode active material accounts for described negative electrode active material layer total weight is 90～99.5 %.
The present invention also provides a kind of lithium ion battery, comprises positive pole, negative pole, is interval in porous polymer barrier film and electrolyte between described positive pole and the described negative pole, and described negative pole is the above-mentioned lithium ion battery negative of mentioning.
With respect to present lithium ion battery negative material system, lithium ion battery negative of the present invention and described lithium ion battery have following characteristics: one, low thermal expansion, owing to having a large amount of polar groups on its molecular structure of water-soluble polymeric binder-polymine, thereby providing stronger bonding force between negative electrode active material layer and the negative current collector and between the negative electrode active material layer internal particle, and the bonding force that forms thus is difficult to be damaged and affects bond effect under the effect of electrolyte.In addition, has the change in volume that viscoelastic water milk type polymer binding agent can be buffered in the active material that produces in the charge and discharge process, even so that after expansion and contraction, also can keep original cohesive force and the electrode interior structure of binding agent.So the structural stability of negative electrode active material layer in the long-term cyclic process of battery kept in both combinations on the whole, reduced the expansion rate of battery.
Two, Low ESR, high magnification, owing to having a large amount of amine polar groups on the polymine molecular structure, the polar group that these electron donations are very strong help to increase lithium salts dissociation and with lithium cation generation complexing, and polymine has lower glass transition temperature, its molecule segment has enough compliances, can help to improve lithium ion in the conduction of electrode interior, reduce the polarization in the charge and discharge process, improve battery efficiency.In addition, the interworking of two kinds of adhesives is used the overall consumption that can reduce inert binder, equally also can realize reducing impedance, improves the effect of battery efficiency.
Three, good long cycle characteristics, except the structural stability of negative electrode active material layer in the long-term cyclic process of battery kept in the combination of two kinds of adhesives on the whole, improved beyond the cyclical stability of battery, a large amount of amidos on the polymine molecular structure can also consume the acidic by-products that electrolyte produces in cyclic process (as, hydrofluoric acid etc.), because these accessory substances can have a strong impact on the stability of circulating battery, so the use of polymine is conducive to the long-term stability that circulates of battery equally from this aspect.
Description of drawings
Fig. 1 is the bounce-back curve chart of battery cathode pole piece thickness in manufacturing process of the embodiment of the invention 1 and Comparative Examples 1.
Fig. 2 be the embodiment of the invention 1 with the battery of Comparative Examples 1 under normal temperature environment discharge capacity to discharge current curves figure.
Fig. 3 is the embodiment of the invention 1 and the battery of Comparative Examples 1 battery core thickness bounce-back rate curve figure during loop test under normal temperature environment.
Fig. 4 is the embodiment of the invention 1 and the battery of Comparative Examples 1 battery core capability retention curve chart during loop test under normal temperature environment.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention and beneficial effect thereof are elaborated, but embodiments of the present invention are not limited to this.
Embodiment 1,A kind of lithium ion battery negative, comprise negative current collector and the negative electrode active material layer of coating negative current collector, negative electrode active material layer comprises negative electrode active material, conductive agent, polymer viscosifier, water milk type polymer binding agent and water-soluble polymeric binder, the water-soluble polymeric binder is polymine, and the weight rate of water milk type polymer binding agent and water-soluble polymeric binder is 10:90 ~ 90:10.
The preparation of negative pole: the cathode size prescription is pressed the siccative weight percent meter, by 2% SBR emulsion, 1.5% polymine, 0.5% sodium carboxymethylcellulose, 1% conductive black, 95% negative electrode active material, five parts form, wherein negative electrode active material adopts Delanium, the weight average molecular weight of polymine is about 500 g/mol, its mass concentration is that the pH value of 5% the aqueous solution is in 9～12 scope, the substitution value of sodium carboxymethylcellulose is in 0.8～1.0 scope, and its mass concentration is that 1% the aqueous solution is in the scope of the viscosity under 25 ℃ at 1000～3000mPa.s.In the slurry layoutprocedure, solvent is deionized water, and water accounts for 60% of total stock quality.
At first by above prescription deionized water and sodium carboxymethylcellulose are joined in the mixer grinder, dissolve complete under vacuum, obtain aqueous polymer solution, by prescription conductive black is added again and dissolved in the good aqueous polymer solution, it is below the 5 μ m that rapid stirring is ground to fineness, then add graphite by prescription, disperse to stir, vacuumize at last and remove bubble.Namely obtain required cathode size with 150 order stainless steel sift net filtrations.
This slurry of making is coated in the Copper Foil two sides that thickness is 8 μ m equably, with roll squeezer pole piece is compacted to certain thickness again, cut-parts, soldering polar ear obtains cathode pole piece.
Preferably, polymine is the homopolymers of aziridine, aziridine mixture or the copolymer of aziridine mixture, wherein also comprises polymine, and the macromolecular structure of polymine comprises line style, branched chain type and hyperbranched type.
Comprise in the large molecule of polymine that primary amino radical, secondary amino group and uncle are amino, with respect to amino total amount, the molar ratio of primary amino radical is more than 20%, and the molar ratio of secondary amino group is more than 20%, and the molar ratio of uncle's amino is in 60%.
Anodal preparation: positive pole selects cobalt acid lithium (LiCoO2) to be active material, according to the prescription preparation anode sizing agent that feeds intake.Press the anode formula design, the slurry solids composition comprises 92% positive active material, 4% Kynoar (PVDF) binding agent, and 4% conductive black.Anode sizing agent uses 1-METHYLPYRROLIDONE (NMP) as dispersion solvent, and the solids content of slurry is 45%.
By the above proportioning 1-METHYLPYRROLIDONE and Kynoar are joined in the mixer grinder, fully stirring and dissolving obtains the polymer solution of Kynoar.By prescription conductive black is added and dissolved in the good polyvinylidene fluoride polymer solution, it is below the 5 μ m that rapid stirring is ground to fineness, then adds cobalt acid lithium by prescription, disperses to stir, and vacuumizes at last and removes bubble.Namely obtain required anode sizing agent with 150 order stainless steel sift net filtrations.
This slurry of making is coated in the aluminium foil two sides that thickness is 12 μ m equably, with roll squeezer pole piece is compacted to certain thickness again, cut-parts, soldering polar ear obtains anode pole piece.
It is polyethylene (PE) perforated membrane of 14 μ m that polymeric barrier films is selected thickness.
The preparation of electrolyte: ethylene carbonate EC, propene carbonate PC and dimethyl carbonate DMC are mixed with mixed solvent according to volume ratio 3:3:4, and then adding lithium salts lithium hexafluoro phosphate (LiPF6), the concentration of preparation LiPF6 is 1M, obtains electrolyte after stirring.
The assembling of battery: above-mentioned anode pole piece, polymeric barrier films and cathode pole piece are wound into battery core, the aluminum-plastic composite membrane encapsulation, the vacuum state baking is injected quantitative electrolyte after removing moisture, battery is changed into and volume test, obtain the square soft-packaged polymer lithium ion battery that thick wide length is respectively 3.6mm, 28mm, 92mm.
A kind of lithium ion battery comprises positive pole, negative pole, is interval in porous polymer barrier film and electrolyte between positive pole and the negative pole, and this negative pole is above-mentioned prepared cathode pole piece.
Embodiment 2,As different from Example 1: the preparation process of the present embodiment negative pole is, the cathode size prescription is pressed the siccative weight percent meter, by 2% acrylonitrile-butadiene rubber latex, 1.5% butadiene rubber emulsion, 2% polymine, 0.5% carboxymethyl cellulose, 1% carbon fiber, 93% negative electrode active material, five parts form, wherein negative electrode active material adopts native graphite and graphitized carbon fibre, the weight average molecular weight of polymine is about 100,000g/mol, its mass concentration is that the pH value of 5% the aqueous solution is in 9～12 scope, the substitution value of carboxymethyl cellulose is in the scope of 0.8-1.0, and its mass concentration is that 1% the aqueous solution is in the scope of the viscosity under 25 ℃ at 1000-3000mPa.s.In the slurry layoutprocedure, solvent is deionized water, and water accounts for 60% of total stock quality.
At first by above prescription deionized water and carboxymethyl cellulose are joined in the mixer grinder, dissolve complete under vacuum, obtain aqueous polymer solution, by prescription carbon fiber is added again and dissolved in the good aqueous polymer solution, it is below the 5 μ m that rapid stirring is ground to fineness, then add native graphite and graphitized carbon fibre by prescription, disperse to stir, vacuumize at last and remove bubble.Namely obtain required cathode size with 150 order stainless steel sift net filtrations.
This slurry of making is coated in the Copper Foil two sides that thickness is 8 μ m equably, with roll squeezer pole piece is compacted to certain thickness again, cut-parts, soldering polar ear obtains cathode pole piece.
Other identical with embodiment 1 no longer repeated here.
Embodiment 3,As different from Example 2: the preparation process of the present embodiment negative pole is, the cathode size prescription is pressed the siccative weight percent meter, by 2% butadiene rubber emulsion, 2% polymine, 1% hydroxyethylcellulose, 1% carbon nano-tube, 94% negative electrode active material, five parts form, wherein negative electrode active material adopts graphitized intermediate-phase carbon microballon and amorphous carbon, the weight average molecular weight of polymine is about 5,000 g/mol, its mass concentration is that the pH value of 5% the aqueous solution is in 9～12 scope, the substitution value of hydroxyethylcellulose is in the scope of 0.8-1.0, and its mass concentration is that 1% the aqueous solution is in the scope of the viscosity under 25 ℃ at 1000-3000mPa.s.In the slurry layoutprocedure, solvent is deionized water, and water accounts for 60% of total stock quality.
At first by above prescription deionized water and hydroxyethylcellulose are joined in the mixer grinder, dissolve complete under vacuum, obtain aqueous polymer solution, by prescription carbon nano-tube is added again and dissolved in the good aqueous polymer solution, it is below the 5 μ m that rapid stirring is ground to fineness, then add graphitized intermediate-phase carbon microballon and amorphous carbon by prescription, disperse to stir, vacuumize at last and remove bubble.Namely obtain required cathode size with 150 order stainless steel sift net filtrations.
This slurry of making is coated in the Copper Foil two sides that thickness is 8 μ m equably, with roll squeezer pole piece is compacted to certain thickness again, cut-parts, soldering polar ear obtains cathode pole piece.
Other identical with embodiment 2 no longer repeated here.
Embodiment 4,As different from Example 3: the preparation process of the present embodiment negative pole is, the cathode size prescription is pressed the siccative weight percent meter, by 2% chloroprene rubber emulsion, 2% polymine, 1% polyacrylic acid, 1% Graphene, 94% negative electrode active material, five parts form, wherein negative electrode active material adopts amorphous carbon, silicon and silica, the weight average molecular weight of polymine is about 20,000 g/mol, its mass concentration is that the pH value of 5% the aqueous solution is in 9～12 scope, polyacrylic substitution value is in the scope of 0.8-1.0, and its mass concentration is that 1% the aqueous solution is in the scope of the viscosity under 25 ℃ at 1000-3000mPa.s.In the slurry layoutprocedure, solvent is deionized water, and water accounts for 60% of total stock quality.
At first by above prescription deionized water and polyacrylic acid are joined in the mixer grinder, dissolve complete under vacuum, obtain aqueous polymer solution, by prescription Graphene is added again and dissolved in the good aqueous polymer solution, it is below the 5 μ m that rapid stirring is ground to fineness, then add amorphous carbon, silicon and silica by prescription, disperse to stir, vacuumize at last and remove bubble.Namely obtain required cathode size with 150 order stainless steel sift net filtrations.
This slurry of making is coated in the Copper Foil two sides that thickness is 8 μ m equably, with roll squeezer pole piece is compacted to certain thickness again, cut-parts, soldering polar ear obtains cathode pole piece.
Other identical with embodiment 3 no longer repeated here.
Embodiment 5,As different from Example 4: the preparation process of the present embodiment negative pole is, the cathode size prescription is pressed the siccative weight percent meter, by 1.5% ethylene-propylene-diene monomer latex solution, 1.5% polymine, 0.5% polyvinyl alcohol, 1% conductive black, 95.5% negative electrode active material, five parts form, wherein negative electrode active material adopts tin oxide, the weight average molecular weight of polymine is about 300,000 g/mol, its mass concentration is that the pH value of 5% the aqueous solution is in 9～12 scope, the substitution value of polyvinyl alcohol is in the scope of 0.8-1.0, and its mass concentration is that 1% the aqueous solution is in the scope of the viscosity under 25 ℃ at 1000-3000mPa.s.In the slurry layoutprocedure, solvent is deionized water, and water accounts for 60% of total stock quality.
At first by above prescription deionized water and polyvinyl alcohol are joined in the mixer grinder, dissolve complete under vacuum, obtain aqueous polymer solution, by prescription conductive black is added again and dissolved in the good aqueous polymer solution, it is below the 5 μ m that rapid stirring is ground to fineness, then add tin oxide by prescription, disperse to stir, vacuumize at last and remove bubble.Namely obtain required cathode size with 150 order stainless steel sift net filtrations.
This slurry of making is coated in the Copper Foil two sides that thickness is 8 μ m equably, with roll squeezer pole piece is compacted to certain thickness again, cut-parts, soldering polar ear obtains cathode pole piece.
Other identical with embodiment 4 no longer repeated here.
Embodiment 6,As different from Example 5: the preparation process of the present embodiment negative pole is, the cathode size prescription is pressed the siccative weight percent meter, by 1.5% acrylic rubber emulsion, 1.5% polymine, 0.5% sodium carboxymethylcellulose, 1% conductive black, 95.5% negative electrode active material, five parts form, wherein negative electrode active material adopts the ashbury metal compound, the weight average molecular weight of polymine is about 1,000,000 g/mol, its mass concentration is that the pH value of 5% the aqueous solution is in 9～12 scope, the substitution value of sodium carboxymethylcellulose is in the scope of 0.8-1.0, and its mass concentration is that 1% the aqueous solution is in the scope of the viscosity under 25 ℃ at 1000-3000mPa.s.In the slurry layoutprocedure, solvent is deionized water, and water accounts for 60% of total stock quality.
At first by above prescription deionized water and sodium carboxymethylcellulose are joined in the mixer grinder, dissolve complete under vacuum, obtain aqueous polymer solution, by prescription conductive black is added again and dissolved in the good aqueous polymer solution, it is below the 5 μ m that rapid stirring is ground to fineness, then add the ashbury metal compound by prescription, disperse to stir, vacuumize at last and remove bubble.Namely obtain required cathode size with 150 order stainless steel sift net filtrations.
This slurry of making is coated in the Copper Foil two sides that thickness is 8 μ m equably, with roll squeezer pole piece is compacted to certain thickness again, cut-parts, soldering polar ear obtains cathode pole piece.
Other identical with embodiment 5 no longer repeated here.
Comparative Examples 1,The cathode size prescription is pressed the siccative weight percent meter, formed by 4% SBR emulsion, 1% sodium carboxymethylcellulose, 1% conductive black, 94% negative electrode active material, four parts, wherein negative electrode active material adopts Delanium, the substitution value of sodium carboxymethylcellulose is in the scope of 0.8-1.0, and its mass concentration is that 1% the aqueous solution is in the scope of the viscosity under 25 ℃ at 1000-3000mPa.s.In the slurry layoutprocedure, solvent is deionized water, and water accounts for 60% of total stock quality.
Other identical with embodiment 1 no longer repeated here.
The present invention carries out following experiment: the cohesive force test in (one) electrode between active material and the adhesive: the cathode pole piece of getting respectively cold pressing rear embodiment 1 to 6 and Comparative Examples 1, every group of 5 pole pieces, be cut into the test bars of 20mm * 10cm size, on measurer for pulling force, it carried out 180 by using the wide green adhesive tape of PET (adhesion strength 0.1N/mm) of 20mm
oPeel off test, the puller system draw speed is 50mm/min.Outcome record is in table 1.
(2) test of the adhesion between active material and the collector in the electrode: the cathode pole piece of getting respectively cold pressing rear embodiment 1 to 6 and Comparative Examples 1, every group of 5 pole pieces, be cut into the test bars of 20mm * 10cm size, stick on the clean corrosion resistant plate with the wide double faced adhesive tape of 20mm (adhesion strength 0.7N/mm).Adopt measurer for pulling force that it is carried out 180
oPeel off test, the puller system draw speed is 50mm/min.Outcome record is in table 1.
(3) membrane resistance of pole piece test: the cathode membrane to embodiment 1 to 6 and Comparative Examples 1 is carried out resistance test, and acquired results is recorded in the table 1.
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As can be seen from Table 1, lithium ion battery negative of the present invention is compared as the negative pole of binding agent with single water milk type polymer after having adopted the compound system of water-soluble, water milk type polymer binding agent, adhesion in cohesive force in the electrode between active material and the adhesive and the electrode between active material and the collector all is significantly improved, and membrane resistance remains at low levels.
(4) the pole piece bounce-back is tested: after the cathode membrane of embodiment 1 to 6 and Comparative Examples 1 is colded pressing, use miking pole piece thickness, and carry out mark in measuring position and pole piece, as the pole piece original depth.In follow-up battery core manufacturing process, successively before pole piece coiling, battery changes into to 3.85V, volume test and completely is charged to several stages such as 4.2V in the situation of change of identical before this position measurement negative plate thickness, calculate the bounce-back rate of negative plate thickness under the different conditions, acquired results is listed in Fig. 1.
As shown in Figure 1, lithium ion battery negative of the present invention is compared as the negative pole of binding agent with single water milk type polymer after having adopted the compound system of water-soluble, water milk type polymer binding agent, and under the same stage bounce-back rate of negative plate thickness decreases.This feature has just guaranteed that also battery core thickness can remain in the design specification, more is conducive to the stable of battery volume energy density.
(5) battery cryogenic property test: the lithium ion battery of getting respectively embodiment 1 and Comparative Examples 1 is sample, under the 10oC environment, with the charge-discharge magnification of 0.7C/0.5C circulation 10 times, completely be charged at last 4.2V, disassemble again battery, observe the lithium situation of analysing on cathode pole piece surface.The result shows: separating out of simple substance lithium metal do not found on the cathode pole piece surface of embodiment 1, the phenomenon that Comparative Examples 1 then has very obvious simple substance lithium metal to separate out.The cathode pole piece of this phenomenon explanation embodiment 1 has better dynamic performance under low-temperature condition.
(6) battery discharge multiplying power test: the lithium ion battery of getting respectively embodiment 1 and Comparative Examples 1 is sample, 25
oWith the charging of 0.5C multiplying power, measure successively the battery capacity of discharging with 0.2C, 0.5C, 1.0C, 2.0C different multiplying under the C environment, acquired results is listed in Fig. 2.As seen from Figure 2, the battery high rate performance of embodiment 1 will be higher than the high rate performance of the battery of Comparative Examples 1.The polarization of cathode pole piece in discharge process of this explanation embodiment 1 is less, has better dynamic performance.
(7) thickness swelling and cycle performance test in the circulating battery process: the lithium ion battery of getting respectively embodiment 1 and Comparative Examples 1 is sample, carry out the test of circulating battery thickness swelling and cycle performance: before the circulating battery, adopt the thickness of height gage test battery under the 3.85V voltage status, be denoted as the battery original thickness.Then 25
oUnder the C environment, with the charge-discharge magnification of 0.7C/0.5C battery is carried out loop test.In the cyclic process, measure battery under first time fully charged state 4.2V voltage, the thickness under the battery fully charged state after per 50 circulations backward is until Fig. 3 is seen in the 500th circulation.Obtain simultaneously capacity attenuation curve in the circulating battery process, see Fig. 4.
Cell expansion rate=(4.2V cell thickness/3.85V battery initial thickness-1) * 100%, as shown in Figure 3: under the same loop number of times, the cell thickness expansion rate of embodiment 1 is significantly less than the battery of Comparative Examples 1.The result shows that the negative pole of embodiment 1 has adopted behind the compound system of water-soluble, water milk type polymer binding agent the combination of two kinds of binding agents to keep better the structural stability of negative electrode active material layer in the long-term cyclic process of battery, has reduced the expansion rate of battery.Simultaneously, as shown in Figure 4: the battery of embodiment 1 has still kept 90% initial capacity later 500 times in circulation, apparently higher than the battery of Comparative Examples 1.As seen, lithium battery of the present invention has better long circulation life.
In sum, lithium ion battery negative of the present invention adopts the butadiene-styrene rubber class to have the interworking system of viscoelastic water milk type polymer binding agent and polyethyleneimine: amine water-soluble polymeric binder, can significantly improve between negative electrode active material layer and the negative current collector and the cohesive force between the negative electrode active material layer internal particle, thereby improve the structural stability of negative electrode active material layer in the long-term cyclic process of battery, and the use amount of the polymeric binder of reduction electrochemistry inertia, thereby reduce the cubical expansivity of battery in cyclic process, improve the low temperature of polymer Li-ion battery, multiplying power, cycle performance and energy density.
The according to the above description announcement of book and instruction, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement, replacement or modification that every those skilled in the art have done on basis of the present invention all belong to protection scope of the present invention.In addition, although used some specific terms in this specification, these terms do not consist of any restriction to the present invention just for convenience of description.
Claims (16)
1. lithium ion battery negative, comprise negative current collector and the negative electrode active material layer of coating described negative current collector, described negative electrode active material layer comprises negative electrode active material, conductive agent, polymer viscosifier, water milk type polymer binding agent and water-soluble polymeric binder, it is characterized in that: described water-soluble polymeric binder is polymine, and the weight rate of described water milk type polymer binding agent and described water-soluble polymeric binder is 10:90 ~ 90:10.
2. lithium ion battery negative according to claim 1 is characterized in that: described water milk type polymer binding agent is at least a in butadiene-styrene rubber, acrylonitrile-butadiene rubber, butadiene rubber, chloroprene rubber, ethylene propylene diene rubber and the acrylic rubber.
3. lithium ion battery negative according to claim 2, it is characterized in that: the percentage by weight that described water milk type polymer binding agent accounts for described negative electrode active material layer total weight is 0.5～10%.
4. lithium ion battery negative according to claim 3, it is characterized in that: the percentage by weight that described water milk type polymer binding agent accounts for described negative electrode active material layer total weight is 0.5～3 %.
5. lithium ion battery negative according to claim 1, it is characterized in that: described polymine is the homopolymers of aziridine, aziridine mixture or the copolymer of aziridine mixture, and the macromolecular structure of described polymine comprises line style, branched chain type and hyperbranched type.
6. lithium ion battery negative according to claim 5, it is characterized in that: the percentage by weight that described polymine accounts for described negative electrode active material layer total weight is 0.5～10 %.
7. lithium ion battery negative according to claim 6, it is characterized in that: the percentage by weight that described polymine accounts for described negative electrode active material layer total weight is 0.5～3 %.
8. lithium ion battery negative according to claim 5, it is characterized in that: the weight average molecular weight of described polymine is 500～1,000,000 g/mol.
9. lithium ion battery negative according to claim 8, it is characterized in that: the weight average molecular weight of described polymine is 5,000～500,000 g/mol.
10. lithium ion battery negative according to claim 5, it is characterized in that: comprise in the large molecule of described polymine that primary amino radical, secondary amino group and uncle are amino, with respect to amino total amount, the molar ratio of primary amino radical is more than 20%, the molar ratio of secondary amino group is more than 20%, and the molar ratio of uncle's amino is in 60%.
11. lithium ion battery negative according to claim 5 is characterized in that: the pH value of the aqueous solution of described polymine 5% concentration is 9～12.
12. lithium ion battery negative according to claim 1 is characterized in that: described negative electrode active material is at least a in native graphite, Delanium, graphitized carbon fibre, graphitized intermediate-phase carbon microballon, amorphous carbon, silicon, silica, tin oxide and the ashbury metal compound.
13. lithium ion battery negative according to claim 1 is characterized in that: described conductive agent is at least a in conductive black, carbon fiber, carbon nano-tube and the Graphene.
14. lithium ion battery negative according to claim 1 is characterized in that: described polymer viscosifier is at least a in sodium carboxymethylcellulose, CMC, hydroxyethylcellulose, polyacrylic acid and the polyvinyl alcohol.
15. lithium ion battery negative according to claim 12 is characterized in that: the percentage by weight that described negative electrode active material accounts for described negative electrode active material layer total weight is 90～99.5%.
16. a lithium ion battery comprises positive pole, negative pole, is interval in porous polymer barrier film and electrolyte between described positive pole and the described negative pole, it is characterized in that: described negative pole is each described lithium ion battery negative of claim 1 to 15.
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