CN103531814A - Composite conductive agent, dispersion method thereof, positive plate and lithium ion battery - Google Patents
Composite conductive agent, dispersion method thereof, positive plate and lithium ion battery Download PDFInfo
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Abstract
The invention discloses a composite conductive agent, a dispersing method thereof, a positive plate and a lithium ion battery, wherein the particle size of each component of the composite conductive agent is distributed in a gradient manner from nano-scale to micron-scale, and the components are as follows by weight percent: 30-40% of nano spherical carbon particle conductive agent; 15-30% of submicron graphite particle conductive agent; 10-20% of micron-sized conductive graphite; 20-30% of nano-scale linear conductive agent. According to the invention, the composite conductive agent is added in the preparation process of the positive plate, and the composite conductive agent is effectively mixed with the positive material particles in the lithium ion battery, so that a three-dimensional network conductive structure is formed in the positive plate, the conductivity of the positive material is greatly improved, the gram specific capacity of the active substance is further improved, and the liquid absorption performance of the positive plate is improved, thereby obviously improving the rate capability, the cycle performance and the low-temperature performance of the lithium ion battery, and ensuring that the lithium ion battery has more excellent safety performance to a certain extent.
Description
Technical field
The present invention relates to energy and material technical field, relate in particular to a kind of combined conductive agent and process for dispersing thereof and a kind of positive plate and lithium ion battery.
Background technology
Lithium ion battery is as new green power, because of its high power capacity, high voltage, small, light, have extended cycle life, the advantage such as working range is wide, fail safe good, memory-less effect, at the portable type electronic product developing rapidly in recent years, be widely used in as 3C/3G mobile phone, notebook computer, panel computer, video camera etc., the various fields such as the power-supply system of electric automobile, national defense and military equipment and photovoltaic energy storage system, energy storage alternate peak power station, uninterrupted power supply, middle-size and small-size energy-storage system have a wide range of applications future.
In the face of power lithium-ion battery, the large-scale application demand of energy storage lithium ion battery, improve the performance of lithium ion battery, it is crucial reducing costs, and further improves power density, the energy density of positive and negative pole material and improve the emphasis that cycle performance, cryogenic property and security performance become development.
The conductive agent adopting in the making of lithium ion battery anode glue size is at present carbon black, acetylene black or Super-P, electrically conductive graphite and carbon nano-tube, carbon nano-fiber etc., and conductive agent mostly is single use, or carbon black, acetylene black are combined use with two kinds of electrically conductive graphite, carbon nano-tube etc.The own specific area of conductive agent carbon black, acetylene black or Super-P is large, and gram specific capacity is low, and generally, below 280mAh/g, often efficiency is low first in its single use, is difficult to improve high rate performance and the cycle performance of battery; Although gram specific capacities such as electrically conductive graphite KS-6, crystalline flake graphite are high, generally, more than 320mAh/g, often because it mostly is micron particles, use separately conductivity limited; Carbon nano-tube is used separately to exist and is difficult to disperse, first the drawback such as efficiency height.Carbon black, acetylene black are combined use with two kinds of electrically conductive graphite, carbon nano-tube etc. and can be played comprehensive effect, as mentioned the binary combined conductive agent compound uses such as carbon nano-tube and conductive black, acetylene black in disclosed CN 103199258 A patents of invention.But simple binary conductive agent compound use can not form effective three-dimensional network conductive structure, and in power, energy storage lithium ion battery, conductive effect is still inadequate.
Therefore, prior art is still further improved and develops.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of combined conductive agent and process for dispersing thereof and a kind of positive plate and lithium ion battery, be intended to solve the undesirable problem of conductive effect in current driving force, energy storage lithium ion battery.
Technical scheme of the present invention is as follows:
A kind of combined conductive agent, wherein, described combined conductive agent is by nano-level sphere carbon granule conductive agent, submicron order graphite granule conductive agent, micron order electrically conductive graphite, nanoscale wire conductive agent compound composition, and each component particles size is from nanoscale to submicron order, then to micron order distribution gradient.Wherein, each components based on weight percentage is:
Nano-level sphere carbon granule conductive agent 30-40%;
Submicron order graphite granule conductive agent 15-30%;
Micron order electrically conductive graphite 10-20%;
Nanoscale wire conductive agent 20-30%.
Described combined conductive agent, wherein, described combined conductive agent is composed of the following components by weight percentage:
Nano-level sphere carbon granule conductive agent 30%;
Submicron order graphite granule conductive agent 20%;
Micron order electrically conductive graphite 20%;
Nanoscale wire conductive agent 30%.
Described combined conductive agent, wherein, described nano-level sphere carbon granule conductive agent is that average grain diameter D50 is a kind of in carbon black, acetylene black and the Super-P of 20-60nm;
Described submicron order graphite granule conductive agent is that average grain diameter D50 is at the submicron graphite particle conductive agent of 300-900nm;
Described micron order electrically conductive graphite is one or more in micron-sized spherical electrically conductive graphite, sheet electrically conductive graphite, crystalline flake graphite;
Described nanometer wire conductive agent is one or more in carbon nano-tube, carbon nano-fiber.
Described combined conductive agent, wherein, gram specific capacity of described submicron order graphite granule conductive agent is more than 340mAh/g;
Gram specific capacity of described micron order electrically conductive graphite is more than 320mAh/g.
The process for dispersing of combined conductive agent as above in lithium ion battery anode glue size, wherein, described process for dispersing is:
In the preparation process of anode sizing agent, in anode sizing agent, add described combined conductive agent and macromolecule dispersing agent to carry out high speed dispersion, recycling mechanical shear stress is further broken up the aggregate in mixed liquor, and combined conductive agent is evenly spread in anode sizing agent.
The process for dispersing of described combined conductive agent in lithium ion battery anode glue size, wherein, described macromolecule dispersing agent is polyvinylpyrrolidone.
, wherein, described positive plate has nanoscale or the submicron order three-dimensional network conductive structure being mixed to form by combined conductive agent as above and positive electrode.
Described positive plate, wherein, described positive electrode is LiFePO
4, LiCoO
2, Li
2mnO
4, Li (Ni
xco
ymn
1-x-y) O
2in any one or a few.
Described positive plate, wherein, the weight mixed proportion of described combined conductive agent and positive electrode is 88-95:1-5.
, wherein, described lithium ion battery comprises positive plate as above.
Beneficial effect: the invention provides a kind of combined conductive agent and process for dispersing thereof and a kind of positive plate and lithium ion battery, the present invention adds combined conductive agent when prepared by positive plate, by it, mix with the effective of positive electrode particle in lithium ion battery, in positive plate, form three-dimensional network conductive structure, greatly improve the electric conductivity of positive electrode, further improved gram specific capacity performance of active material, improve the absorbent of positive plate, thereby significantly improve the high rate performance of lithium ion battery, cycle performance and cryogenic property, also guaranteed to a certain extent that lithium ion battery has more excellent security performance.
Accompanying drawing explanation
Fig. 1 is material structure schematic diagram in based lithium-ion battery positive plate of the present invention.
Fig. 2 is 1C cycle performance curve under the polymer ferric phosphate lithium cell normal temperature of the embodiment of the present invention 2 preparation.
Fig. 3 is the performance comparison figure of the polymer ferric phosphate lithium cell of embodiment of the present invention 1-3 and comparative example 1 preparation.
Fig. 4 is the polymer ferric phosphate lithium cell discharge-rate performance comparison figure of embodiment 1 and comparative example 1 preparation.
Embodiment
The invention provides a kind of combined conductive agent and process for dispersing thereof and a kind of positive plate and lithium ion battery, for making object of the present invention, technical scheme and effect clearer, clear and definite, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
A kind of combined conductive agent, described combined conductive agent is by nano-level sphere carbon granule conductive agent, submicron order graphite granule conductive agent, micron order electrically conductive graphite, nanoscale wire conductive agent compound composition, and each component particles size is from nanoscale to submicron order, then to micron order distribution gradient.Wherein, each components based on weight percentage is:
Nano-level sphere carbon granule conductive agent 30-40%;
Submicron order graphite granule conductive agent 15-30%;
Micron order electrically conductive graphite 10-20%;
Nanoscale wire conductive agent 20-30%.
In preferred embodiment, described combined conductive agent is composed of the following components by weight percentage:
Nano-level sphere carbon granule conductive agent 30%;
Submicron order graphite granule conductive agent 20%;
Micron order electrically conductive graphite 20%;
Nanoscale wire conductive agent 30%.
Wherein, described nano-level sphere carbon granule conductive agent is that average grain diameter D50 is at carbon black, acetylene black and the Super-P(granule conductive black of 20-60nm) in a kind of.Described submicron order (or being called flake nano) graphite granule conductive agent is that average grain diameter D50 is at the submicron graphite particle conductive agent of 300-900nm.Described micron order electrically conductive graphite is for example, in micron-sized spherical electrically conductive graphite, sheet electrically conductive graphite (KS-6), crystalline flake graphite one or more.Described nanometer wire conductive agent is one or more in carbon nano-tube, carbon nano-fiber.
In preferred embodiment, himself gram specific capacity of described submicron order graphite granule conductive agent is more than 340mAh/g.Himself gram specific capacity of described micron order electrically conductive graphite is more than 320mAh/g.
Wherein average grain diameter D50 can be effectively at 20-60nm nano-level sphere carbon granule and micron order electrically conductive graphite at 300-900nm submicron order graphite granule conductive agent, between nanoscale wire conductive agent, be built into conductiving point, compensation nano-level sphere carbon granule and micron order electrically conductive graphite, conductive gap between nanometer wire conductive agent, form effective three-dimensional network conductive structure, thereby greatly improve the electric conductivity of positive electrode, add that average grain diameter D50 is very high in itself gram specific capacity of 300-900nm submicron order graphite granule conductive agent, more than 340mAh/g, can further improve gram specific capacity performance of active material, be conducive to improve the absorbent of positive plate simultaneously, significantly improve high rate performance, cycle performance and the cryogenic property of lithium ion battery, also guaranteed to a certain extent that lithium ion battery has more excellent security performance.
The process for dispersing of combined conductive agent as above in lithium ion battery anode glue size, wherein, described process for dispersing is for adopting the ultra-fine dispersion technology of nanometer effectively to disperse, be specially: in the preparation process of anode sizing agent, in anode sizing agent, add described combined conductive agent and macromolecule dispersing agent polyvinylpyrrolidone and carry out high speed dispersion by high viscosity dispersator, the strong machine mechanical shear stress that recycles ultra-fine dispersing apparatus is further broken up the aggregate in mixed liquor, obtain enough tiny powder granule, and be uniformly distributed in solution, combined conductive agent is evenly spread in anode sizing agent, thereby reach the effect of the ultra-fine dispersion of nanometer.
, wherein, described positive plate has nanoscale or the submicron order three-dimensional network conductive structure being mixed to form by combined conductive agent as above and positive electrode.Wherein, described positive electrode is LiFePO
4, LiCoO
2, Li
2mnO
4, Li (Ni
xco
ymn
1-x-y) O
2in any one or a few.As shown in Figure 1, in described positive plate, by positive electrode 1, nanoscale wire conductive agent 2, micron order electrically conductive graphite 3, nano-level sphere carbon granule conductive agent 4, submicron order graphite granule conductive agent 5, form nanoscale or submicron order three-dimensional network conductive structure.Wherein positive electrode 1 is the inner anode active material of lithium ion battery micron particles that contains nanoscale or submicron order three-dimensional network conductive structure.
In described positive plate, the weight mixed proportion of described combined conductive agent and positive electrode is 88-95:1-5.
Preferably, the present invention adopts 1-METHYLPYRROLIDONE (NMP) as solvent, according to positive electrode: combined conductive agent: it is that 65% slurry is uniformly coated on and forms positive plate on metal aluminum foil that the part by weight of polyvinylidene fluoride (PVDF)=92:3:5 is mixed with solid content.
A kind of lithium ion battery, comprise positive plate, negative plate (in negative plate, negative material is graphite, lithium titanate, silicon-carbon alloy etc.), barrier film, electrolyte and Package casing (aluminum hull, plastic-aluminum packaging film etc.), wherein, described positive plate is the positive plate that nanoscale or submicron order three-dimensional network conductive structure are contained in inside of the present invention.
In preferred embodiment, negative plate can adopt deionized water as solvent, according to Delanium: conductive agent Super-P:SBR(butadiene-styrene rubber): the weight ratio of CMC(sodium carboxymethylcellulose)=94:2:2:2 is mixed with solid content and is uniformly coated on metal copper foil and forms at 45% slurry.Preferably the LiPF that, electrolyte is 1.2mol/L
6solution, solvent is dimethyl carbonate and ethylene sulfite, the volume ratio of solvent is 70%:30%.
The positive plate of making, negative plate and barrier film are wound into battery core, through entering shell, closedtop, fluid injection, change into, the operation such as moulding, detection makes lithium ion battery finished product.
The combined conductive agent that the present embodiment adopts is comprised of at the spherical electrically conductive graphite KS-6 of 5 μ m and the carbon nano-tube of 500nm-5 μ m at submicron order graphite granule conductive agent, the D50 of 600nm at carbon black, the D50 of 20-60nm D50, and the percentage by weight of its shared combined conductive agent is respectively: 40%, 15%, 15%, 30%.
Combined conductive agent adopts the ultra-fine dispersion technology of nanometer effectively to disperse in the preparation process of anode sizing agent, specifically refer to and in the dispersion process of combined conductive agent, introduce macromolecule dispersing agent polyvinylpyrrolidone, with high viscosity dispersator, carry out high speed dispersion, again under the strong mechanical shear stress effect of ultra-fine dispersing apparatus, the aggregates such as fine powder ball in solution are further broken up, obtain enough tiny powder granule, and be uniformly distributed in solution, thereby reach the effect of the ultra-fine dispersion of nanometer, form three-dimensional network conductive structure.
The present embodiment positive plate adopts 1-METHYLPYRROLIDONE (NMP) as solvent, according to positive electrode LiFePO
4: the present embodiment combined conductive agent: it is that 65% slurry is uniformly coated on metal aluminum foil that the ratio of polyvinylidene fluoride (PVDF)=92:3:5 is mixed with solid content.
Negative plate adopts deionized water as solvent, according to Delanium: conductive agent Super-P:SBR(butadiene-styrene rubber): CMC(sodium carboxymethylcellulose)=94:2:2:2 is mixed with solid content and is uniformly coated on metal copper foil at 45% slurry.Electrolyte is the LiPF of 1.2mol/L
6solution, solvent is dimethyl carbonate and ethylene sulfite, the volume ratio of solvent is 70%:30%.
The positive plate of making, negative plate and barrier film are wound into battery core, through entering shell, closedtop, fluid injection, change into, the operation such as moulding, detection makes flexible package polymer ferric phosphate lithium cell.
Embodiment 2
The sub-micro three-dimensional network combined conductive agent of receiving that the present embodiment adopts is comprised of at the spherical electrically conductive graphite KS-6 of 3 μ m and the carbon nano-fiber of 500nm-6 μ m at submicron order graphite granule conductive agent, the D50 of 400nm at acetylene black, the D50 of 20-60nm D50, and the percentage by weight of its shared combined conductive agent is respectively: 30%, 20%, 20%, 30%.
Anode sizing agent formula and preparation method are with embodiment 1, and just conductive agent adopts the combined conductive agent of the present embodiment; Negative plate, barrier film, electrolyte and Package casing are with embodiment 1.
Embodiment 3:
The sub-micro three-dimensional network combined conductive agent of receiving that the present embodiment adopts is comprised of at the spherical electrically conductive graphite KS-6 of 7 μ m and the carbon nano-fiber of 500nm-4 μ m at submicron order (or being called flake nano) graphite granule conductive agent, the D50 of 900nm at Super-P, the D50 of 20-60nm D50, and the percentage by weight of its shared combined conductive agent is respectively: 35%, 30%, 10%, 25%.
Anode sizing agent formula and preparation method are with embodiment 1, and just conductive agent adopts the combined conductive agent of the present embodiment; Negative plate, barrier film, electrolyte and Package casing are with embodiment 1.
Comparative example 1
The conductive agent that this comparative example 1 adopts is that D50 is at the Super-P of 20-60nm.
Anode sizing agent formula and preparation method are with embodiment 1, and just conductive agent adopts the Super-P conductive agent of this comparative example; Negative plate, barrier film, electrolyte and Package casing are with embodiment 1.
To the 1C cycle performance test at normal temperatures of the polymer ferric phosphate lithium cell of preparation in embodiment 2, be illustrated in figure 2 tested cycle performance curve, from curve, can find out, circulate after 300 times, battery capacity conservation rate, still 98.3%, has very excellent cycle performance.
Above embodiment and the prepared lithium ion battery of comparative example are carried out to performance test, and test result as shown in Figure 3.The battery that as can be seen from Figure 3 prepared by embodiment 1-3 has higher discharge capacity compared to comparative example 1, more excellent cycle performance, better cryogenic property and high rate performance.
Polymer ferric phosphate lithium cell to embodiment 1 and comparative example 1 preparation has carried out discharge-rate performance test, test result as shown in Figure 4, the battery that can find out embodiment 1 preparation from Fig. 4 data, compared to comparative example 1, has higher discharge capacity and high rate performance.
The invention provides a kind of combined conductive agent and process for dispersing thereof and a kind of positive plate and lithium ion battery, the present invention by adding combined conductive agent when prepared by positive plate, by it, effectively mix with positive electrode particle in lithium ion battery, in positive plate, form three-dimensional network conductive structure, greatly improve the electric conductivity of positive electrode, further improved gram specific capacity performance of active material, improve the absorbent of positive plate, thereby significantly improve the high rate performance of lithium ion battery, cycle performance and cryogenic property, also guaranteed to a certain extent that lithium ion battery has more excellent security performance.
Should be understood that; the foregoing is only the preferred embodiments of the present invention; be not sufficient to limit technical scheme of the present invention; for those of ordinary skills; within the spirit and principles in the present invention, can be increased and decreased according to the above description, replaced, converted or be improved, and all these increases and decreases, replace, conversion or improve after technical scheme; all should belong to the scope of the technology of the present invention feature, within being all included in protection scope of the present invention.
Claims (10)
1. a combined conductive agent, it is characterized in that, described combined conductive agent is by nano-level sphere carbon granule conductive agent, submicron order graphite granule conductive agent, micron order electrically conductive graphite, nanoscale wire conductive agent compound composition, and each component particles size is from nanoscale to submicron order, then to micron order distribution gradient;
Wherein, each components based on weight percentage is:
Nano-level sphere carbon granule conductive agent 30-40%;
Submicron order graphite granule conductive agent 15-30%;
Micron order electrically conductive graphite 10-20%;
Nanoscale wire conductive agent 20-30%.
2. combined conductive agent according to claim 1, is characterized in that, described combined conductive agent is composed of the following components by weight percentage:
Nano-level sphere carbon granule conductive agent 30%;
Submicron order graphite granule conductive agent 20%;
Micron order electrically conductive graphite 20%;
Nanoscale wire conductive agent 30%.
3. combined conductive agent according to claim 1, is characterized in that, described nano-level sphere carbon granule conductive agent is that average grain diameter D50 is a kind of in carbon black, acetylene black and the Super-P of 20-60nm;
Described submicron order graphite granule conductive agent is that average grain diameter D50 is at the submicron graphite particle conductive agent of 300-900nm;
Described micron order electrically conductive graphite is one or more in micron-sized spherical electrically conductive graphite, sheet electrically conductive graphite, crystalline flake graphite;
Described nanometer wire conductive agent is one or more in carbon nano-tube, carbon nano-fiber.
4. combined conductive agent according to claim 3, is characterized in that, gram specific capacity of described submicron order graphite granule conductive agent is more than 340mAh/g;
Gram specific capacity of described micron order electrically conductive graphite is more than 320mAh/g.
5. the process for dispersing of the combined conductive agent as described in claim 1-4 any one in lithium ion battery anode glue size, is characterized in that, described process for dispersing is:
In the preparation process of anode sizing agent, in anode sizing agent, add described combined conductive agent and macromolecule dispersing agent to carry out high speed dispersion, recycling mechanical shear stress is further broken up the aggregate in mixed liquor, and combined conductive agent is evenly spread in anode sizing agent.
6. the process for dispersing of combined conductive agent according to claim 5 in lithium ion battery anode glue size, is characterized in that, described macromolecule dispersing agent is polyvinylpyrrolidone.
7. a positive plate, is characterized in that, described positive plate has nanoscale or the submicron order three-dimensional network conductive structure being mixed to form by the combined conductive agent described in claim 1-4 any one and positive electrode.
8. positive plate according to claim 7, is characterized in that, described positive electrode is LiFePO
4, LiCoO
2, Li
2mnO
4, Li (Ni
xco
ymn
1-x-y) O
2in any one or a few.
9. positive plate according to claim 7, is characterized in that, the weight mixed proportion of described combined conductive agent and positive electrode is 88-95:1-5.
10. a lithium ion battery, is characterized in that, described lithium ion battery comprises the positive plate as described in claim 7-9 any one.
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| CN103887556A (en) * | 2014-03-13 | 2014-06-25 | 深圳格林德能源有限公司 | Power energy storage polymer lithium ion battery and preparation method thereof |
| CN106229030A (en) * | 2016-07-08 | 2016-12-14 | 中南大学 | A kind of electrically conductive composition, electrically conductive ink, conducting film, preparation method and application |
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| CN113964293A (en) * | 2021-09-23 | 2022-01-21 | 宁波二黑科技有限公司 | Cyclic stable quick-charging type lithium ion battery cathode and application thereof |
| CN114023969A (en) * | 2021-11-03 | 2022-02-08 | 合肥国轩高科动力能源有限公司 | A 3D creeper-type high-performance conductive agent and its preparation method and application |
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| CN113964293B (en) * | 2021-09-23 | 2023-02-28 | 宁波二黑科技有限公司 | Cyclic stable quick-charging type lithium ion battery cathode and application thereof |
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