CN103794754A - Composite negative electrode and preparation method thereof as well as electrochemical power source and application thereof - Google Patents
Composite negative electrode and preparation method thereof as well as electrochemical power source and application thereof Download PDFInfo
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Abstract
The invention provides a composite negative electrode and a preparation method thereof as well as a lithium battery. The composite negative electrode comprises one layer or more than two layers of porous current collectors which are combined in a laminating manner, wherein holes of the porous current collectors are filled with active fillers; the active filler contains a binding material, a conductive agent and an active substrate having lithium ion implanting capability; the weight of the active substance accounts for 80-98% of the total weight of the active filler. The preparation method of the composite negative electrode comprises preparation of sizing agents containing the active substances and injection of the sizing agents. The lithium battery contains the composite negative electrode. The composite negative electrode has stable volume and is high in capacity; the preparation method is simple in process and high in production efficiency, conditions are easy to control, and production cost is reduced. The lithium battery has large-current charge and discharge characteristics and also has characteristics of high specific energy and power.
Description
Technical field
The invention belongs to battery technology field, be specifically related to a kind of Compound Negative electrode and preparation method thereof, electrochemical power source and application thereof.
Background technology
Existing lithium ion battery is most adopts graphite negative electrodes material, and active material is coated on a plane Copper Foil collector.Though graphite material is because the volumetric expansion that charging occurs only has 10% left and right, even if go through hundreds of time cycle charge-discharge, active material and collector still can keep good electrically contacting, but in order to pursue high-energy-density density, the coating thickness of pole piece even exceedes 100 microns up to tens microns.So just have the distance of active material and the collector on pole piece surface, electric transmission path length, can only discharge and recharge with less electric current battery, and the power density of battery is lower, and the charging interval needs several hours.
Pass through in addition vicennial development, the actual capacity (approximately 350 ~ 360mAh/g) of existing graphite material has approached its theoretical capacity (372mAh/g), and the space that capacity promotes is very limited.And the appearance of the emerging electronic product such as smart mobile phone, make traditional lithium ion battery can not meet the standby electric demand of these electronic products, the mankind are badly in need of exploitation and are had the more standby electric battery product of high-energy-density and meet the mankind and use smart mobile phone to enjoy a trip to the dream of network.
The materials such as Si, Sn, Al, Sb, Ge, Zn, Pb, Mg, Na are owing to having higher specific capacity (if the theoretical capacity of Si negative pole is up to 4200mAh/g, 10 times of graphite) and become the first-selection of high specific energy negative active core-shell material, but can there is huge Volumetric expansion (as silicium cathode cubical expansivity exceedes 300%) owing to embedding lithium ion in them, must overcome or suppress this Volumetric expansion and can make these novel high specific energy electrode materials obtain real application.
In order to slow down the Volumetric expansion of these materials, researcher and material manufacturer are prepared into the materials such as Si, Sn, Al, Sb, Ge, Zn, Pb, Mg, Na the nano material of the high-ratio surfaces such as nano particle, nano wire, nanofiber, then are coated on plane Copper Foil collector.The material of nanoscale has higher specific capacity.But due to the reunion of nano material and the volumetric expansion of material, efflorescence can occur active material, and come off from existing plane Copper Foil collector, the cycle life of battery does not reach application requirements.
Separately there is scholar to utilize acetylene black flexible current-collecting body to prepare the combination electrode of silicium cathode.Concrete preparation method is as follows: first carbon coated Si, conductive carbon black and binding agent are modulated into slurry, be applied to membrane surface and dry and obtain the coated silicon layer of carbon, again the slurry containing acetylene black and binding agent is coated with or is sprayed to the coated silicon surface of carbon, after oven dry, obtain a kind of lithium ion battery negative.For the silica-base material changing for large volume in charge and discharge process, this negative pole take acetylene black as flexible current-collecting body is compared with the traditional negative pole take Copper Foil as collector, and cyclical stability has obtained showing and improved.But the strength ratio of this flexible current-collecting body is poor, if be prepared into battery, in preparation process, cannot carry out machinery and reel.And due to intensity difference, easily there is the distortion of pole piece in inside battery, cause battery outward appearance generation deformation, even can destroy the outward appearance of mobile phone.
Industry Ye You company utilizes bubble hydrogen template synthesis porous current collector, and then on-the-spot deposit tin is prepared combination electrode.Its preparation method comprises the following steps: first, adopt bubble hydrogen template synthesis to go out porous current collector; Then, adopt composite electroplating on porous current collector, to deposit kamash alloy and carbon nano-tube, obtain porous current collector/tin-base alloy/carbon nano-tube integrated electrode.But the method preparation process more complicated, it needs on-the-spot electro-deposition ashbury metal and carbon nano-tube, and electrode deposition thickness is less, and the specific energy increase rate of battery is little, and the preparation efficiency of electrode is low.
Summary of the invention
The object of the embodiment of the present invention is to overcome the above-mentioned deficiency of prior art, and a kind of volume stability is provided, the Compound Negative electrode that capacity is high.
Another object of the embodiment of the present invention is to provide the preparation method of the simple Compound Negative electrode of a kind of technique.
The another object of the embodiment of the present invention is to provide a kind of energy high current charge-discharge, takes into account electrochemical power source and the application thereof of high-energy-density and power.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of Compound Negative electrode, comprise the porous current collector of one deck or two-layer above stacked combination, in the hole of described porous current collector, be filled with active fillers, described active fillers contains bonding agent, conductive agent and has the active material that embeds lithium ion ability, and it is 80～98% that described active material accounts for described active fillers total weight percent.
Preferably, above-mentioned active material is at least one in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle of M element, or described active material is at least one and the compound of carbon in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle of M element; Wherein, described M element is at least one in Si, Sn, Al, Sb, Ge, Zn, Pb, Mg, Na.
Particularly, in the time that above-mentioned active material is the compound of at least one and carbon in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle of M element, at least one in described compound in the nano simple substance particle of M element, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle and carbon compound in, the weight content of described M element activity material in described compound is 10 ~ 98%.
Particularly, the particle diameter of above-mentioned nano simple substance particle, nano-oxide particles or Nanoalloy particle is 1～800nm.
Preferably, the number of plies of above-mentioned porous current collector is 1～20 layer.
Particularly, above-mentioned porous current collector is nickel foam, foam copper, foamed aluminium, foamy carbon, Stainless Steel net, nickel screen, copper mesh or aluminium net.
And the preparation method of above-mentioned Compound Negative electrode, comprises the steps:
By described conductive agent, binding agent and described in there is the active material that embeds lithium ion ability and be dispersed in water-based or oil-based solvent, preparation is containing the slurry of active material; Wherein, the weight ratio of described active material, conductive agent, binding agent is 100:(0～15): (1～15), the content of described active material in described slurry is 20%～70%;
Described slurry is injected to the hole of a slice porous current collector, dry, obtain described Compound Negative electrode; Or described slurry is injected to the hole of at least two porous current collectors, dry, then by dried described porous current collector carry out stacked and through hot pressing, roll or/and sintering processes integrally combines, obtain described Compound Negative electrode.
Preferably, above-mentioned slurry to inject the mode of the hole of porous current collector be cast, deposition, apply, spraying, soak, one or more combination of printing.
Preferably, above-mentioned aqueous solvent is at least one in pure water, distilled water, running water; Oil-based solvent is at least one in 1-METHYLPYRROLIDONE, ethanol, propyl alcohol, cyclohexane.
The embodiment of the present invention also provides a kind of electrochemical power source, comprises above-mentioned Compound Negative electrode.
Preferably, the chemical lithium battery that above-mentioned electrochemical power source is electrochemical reaction or the compound lithium capacitor of electrochemical reaction.
Particularly, above-mentioned chemical lithium battery is lithium ion battery, lithium polymer battery, lithium-sulfur cell or lithium-air battery; Compound lithium capacitor is lithium-ion capacitor.
And, the application of above-mentioned electrochemical power source in mobile terminal product, electric automobile, electrical network, communication equipment and/or electric tool.
Particularly, above-mentioned communication equipment comprises operational module and supply module, and described supply module comprises described electrochemical power source, the chemical lithium battery that described electrochemical power source is electrochemical reaction; Described supply module provides electric energy for described operational module, the electric energy operation that described operational module uses described supply module to provide.
Above-mentioned Compound Negative electrode will have in the loose structure (hole) of active material embedding porous current collector that embeds lithium ion ability, like this, this loose structure can effectively suppress the volumetric expansion that active material occurs due to embedding lithium ion, and then avoid occurring powder of detached, thereby strengthen electrically contacting and Compound Negative electrode capacity of active material and collector.Simultaneously, this active material is dispersed in the loose structure of collector, the powder phenomenon-tion that can effectively avoid occurring to reunite between the particle of active material and occur, strengthen the intensity that active material is combined with collector, thereby guarantee the specific capacity that active material is high, extended cycle life and the capacity of this Compound Negative electrode.In addition, above-mentioned Compound Negative electrode adopts the porous current collector with loose structure, has strengthened its mechanical strength, conveniently it is carried out to machinery and reels, and has strengthened the stability of its shape.
The preparation method of above-mentioned Compound Negative electrode only need be mixed with slurry by the active material with embedding lithium ion ability, then be directly injected in the loose structure of collector and be dried, or further dried collector is carried out hot pressing, rolled or/and sintering processes can make this Compound Negative electrode.This preparation method's technique is simple, and condition is easily controlled, and production efficiency is high, has reduced production cost, has effectively avoided existing employing electrodeposition process to produce existing in combination electrode complex process, production efficiency is low, cost is high, the specific energy of battery is low deficiency.
Above-mentioned electrochemical power source is owing to containing above-mentioned Compound Negative electrode, high just because of this Compound Negative electrode capacity, therefore, has given this electrochemical power source specific energy as high in lithium battery.In addition, above-mentioned Compound Negative electrode volume stability in charge and discharge process, therefore, has given the stable circulation performance of this electrochemical power source excellence, and the cycle life that has extended this electrochemical power source, has strengthened the fail safe of this electrochemical power source.Simultaneously, because the above-mentioned active material in above-mentioned Compound Negative electrode embeds in the loose structure of collector, make the distance of this active material and collector short, shortened electric transmission path short, make this electrochemical power source there is large current density electrical characteristics and high power.There is this excellent properties just because of this electrochemical power source, thereby expanded the range of application of this electrochemical power source.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the structural representation of embodiment of the present invention Compound Negative electrode;
Fig. 2 is the cross-sectional structure schematic diagram of Compound Negative electrode described in Fig. 1;
Fig. 3 is a kind of preferred structure schematic diagram of embodiment of the present invention Compound Negative electrode;
Fig. 4 is the another kind of preferred structure schematic diagram of embodiment of the present invention Compound Negative electrode;
Fig. 5 is another preferred structure schematic diagram of embodiment of the present invention Compound Negative electrode;
Fig. 6 is the process chart of embodiment of the present invention Compound Negative electrode preparation method;
Fig. 7 is the cycle performance Data Comparison figure of battery in embodiment 1-3 and comparison example.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Example of the present invention provides a kind of energy volume stability, the Compound Negative electrode that capacity is high, and its structure is as shown in Figure 1, 2.This Compound Negative electrode comprises n (n is integer, and 1≤n≤20) layer porous current collector 1, in the hole 2 of every layer of porous current collector 1, is filled with active fillers 3.Wherein, this active fillers 3 contains bonding agent, conductive agent and has the active material that embeds lithium ion ability, and it is 80～98% that this active material accounts for active fillers 3 total weight percent.Like this, this porous current collector 1 can be one deck, can be also two-layer more than, therefore, this Compound Negative electrode can be at least following structure:
As one embodiment of the invention, Compound Negative electrode contains one deck (being n=1) porous current collector 1, and its structure as shown in Figure 3.In the hole 2 of this porous current collector 1, fill the above-mentioned active fillers 3 that has, as described in Figure 2.
As another embodiment of the present invention, Compound Negative electrode contains two-layer (being n=2) porous current collector 1, i.e. porous current collector 11 and porous current collector 12, and this porous current collector 11 and mutual stacked being combined as a whole of porous current collector 12, its structure is as shown in Figure 4.The structure of this porous current collector 11,12 as described in Figure 2, is all filled with above-mentioned active fillers 3 in the hole 2 of this porous current collector 11,12.Wherein, combination described in the Compound Negative electrode preparation method that the stacked combination between porous current collector 11 and porous current collector 12 vide infra, as hot pressing, roll, the combination such as sintering processes.
As further embodiment of this invention, Compound Negative electrode is containing three layers of (being n=3) porous current collector 1, be porous current collector 11, porous current collector 12 and porous current collector 13, this porous current collector 11, porous current collector 12 and mutual stacked being combined as a whole of porous current collector 13, its structure is as shown in Figure 5.The structure of this porous current collector 11,12 and 13 as described in Figure 2, is all filled with active fillers 3 in the hole 2 of this porous current collector 11,12 and 13.Wherein, active fillers 3 is described above, combination described in the Compound Negative electrode preparation method that the stacked combination between porous current collector 11,12 and 13 vide infra.
In the time of 4≤n≤20, the structure of above-mentioned Compound Negative electrode can be referring to the structure of the Compound Negative electrode of said n=2 or 3 o'clock, and each layer of porous current collector 1 is stacked being combined as a whole.Wherein, in each layer of porous current collector 1, structure as described in Figure 2, is all filled with active fillers 3 in the hole 2 of porous current collector 1, and active fillers 3 contains the active material that embeds lithium ion ability that has that to account for active fillers 3 total weight percent be 80～98%.In addition, combination described in the Compound Negative electrode preparation method that the stacked combination between porous current collector 11 and porous current collector 12 vide infra, as hot pressing, roll, the combination such as sintering processes.
Preferably, said n is 3～5.The number of plies of this preferred collector 1 can make above-mentioned Compound Negative electrode active fillers 3 in the process of preparation can better inject the hole 2 of collector 1, make hole 2 filling active fillers 3 as much as possible, be also conducive to the stacked combination of above-mentioned Compound Negative electrode each layer of collector in the process of preparation simultaneously.
Particularly, the porous current collector 1 in the various embodiments described above is preferably nickel foam, foam copper, foamed aluminium, foamy carbon, Stainless Steel net, nickel screen, copper mesh or aluminium net.This preferred collector 1 has loose structure, and this loose structure is convenient to be embedded above-mentioned active fillers 3 in the hole of loose structure.As nickel foam, foam copper, foamed aluminium, foamy carbon have abundant three-dimensional loose structure, after active fillers 3 is embedded wherein, what make that active fillers 3 is combined with nickel foam, foam copper, foamed aluminium, foamy carbon is tightr, firmly, thereby effectively suppress active material because powder of detached occurs in the volumetric expansion that embedding lithium ion occurs, thereby strengthened electrically contacting of active material and porous current collector 1.
Active fillers 3 in the various embodiments described above is as mentioned above, contains to account for its total weight percent and be preferably 80～98% the active material that embeds lithium ion ability that has.In further preferred embodiment, it is 88～95% that the content of this active material accounts for active fillers 3 total weight percent.Inventor finds under study for action, and suitable change active material, at the content of active fillers 3, can change the capacity of the various embodiments described above Compound Negative electrode significantly.
Particularly, as embodiments of the invention, above-mentioned active material is preferably at least one in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle of M element; Or described active material is preferably at least one and the compound of carbon in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle of M element; Wherein, described M element is at least one in Si, Sn, Al, Sb, Ge, Zn, Pb, Mg, Na; In the time that active material is the compound of at least one and carbon in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle of M element, the weight content of at least one in the nano simple substance particle of described M element, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle in this compound is preferably 10 ~ 98%.This preferred active material has high specific capacity, after being embedded in the porous 2 of porous current collector 1, can effectively suppress by porous current collector 1 volumetric expansion that this preferred active material occurs due to embedding lithium ion, and give the specific capacity that this Compound Negative electrode is higher.
Further, inventor also finds under study for action, and the above-mentioned particle size with the active material that embeds lithium ion ability is controlled to certain limit, can further improve the specific capacity of this active material.In a preferred embodiment, the particle diameter of this above-mentioned nano simple substance particle, nano-oxide particles, Nanoalloy particle is 1～800nm, more preferably 80～200nm.Nano wire, nanotube, nanofiber, nano thin-film are all selected the model of this area routine.
Certainly, above-mentioned active fillers 3, except containing the above-mentioned active material with embedding lithium ion ability, also contains bonding agent, conductive agent.As preferred embodiment, this bonding agent, conductive agent and the above-mentioned weight ratio having between the active material three who embeds lithium ion ability are (1 ~ 15): (0 ~ 15): 100 wherein, adding of conductive agent can be together with this active material, strengthens above-mentioned Compound Negative electrode charge and discharge performance; Bonding agent add the bond strength having strengthened between active fillers 3 and between active fillers 3 and porous current collector 1, avoided active fillers 3 to come off from the hole 2 of porous current collector 1.This bonding agent is preferably at least one in sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR), polyvinylidene fluoride (PVDF); Conductive agent is preferably at least one in SP conductive agent, vapor-grown carbon fibers (VGCF), carbon nano-tube (CNTs), Graphene (Graphene).Certainly, the kind of bonding agent and conductive agent can also adopt this area conventional other bonding agents and conductive agent.
From the above mentioned, Compound Negative electrode in above-described embodiment will have in the loose structure of active material embedding porous current collector that embeds lithium ion ability, like this, this loose structure can effectively suppress the volumetric expansion that active material occurs due to embedding lithium ion, and then avoid occurring powder of detached, thereby strengthen electrically contacting and Compound Negative electrode capacity of active material and collector.Simultaneously, this active material is dispersed in the loose structure of collector, the powder phenomenon-tion that can effectively avoid occurring to reunite between the particle of active material and occur, strengthen the intensity that active material is combined with collector, thereby guarantee the specific capacity that active material is high, extended cycle life and the capacity of this Compound Negative electrode.In addition, above-mentioned Compound Negative electrode adopts the porous current collector with loose structure, has strengthened its mechanical strength, conveniently it is carried out to machinery and reels, and has strengthened the stability of its shape.
Example of the present invention also provides a kind of technique simple above-mentioned Compound Negative electrode preparation method.This Compound Negative electrode preparation method technological process refers to Fig. 5, and simultaneously referring to Fig. 1 and 2, this Compound Negative electrode preparation method comprises the steps:
S01. preparation contains the slurry of active material: conductive agent, binding agent and the above-mentioned active material with embedding lithium ion ability are dispersed in water-based or oil-based solvent, and preparation is containing the slurry of active material; Wherein, the weight ratio of this bonding agent, conductive agent and active material is (1 ~ 15): (0 ~ 15): 100, and in this slurry, the content of active material is 20～70%;
S02. inject slurry: the slurry of step S01 preparation is injected to the hole 2 of a slice porous current collector 1, dry, obtain described Compound Negative electrode; Or the slurry of step S01 preparation is injected to the hole 2 of at least two porous current collectors 1, dry, then by this porous current collector 1 carry out stacked after through hot pressing, roll or/and sintering processes integrally combines, obtain described Compound Negative electrode.
Particularly, as preferred embodiment, in above-mentioned steps S01, the method that conductive agent, binding agent and active material are dispersed in water-based or oil-based solvent is: first conductive agent, binding agent are dispersed in water-based or oil-based solvent, form conducting resinl, and then active material is dispersed in conducting resinl, thereby be mixed with dispersed, and stable slurry.This dispersed, stable slurry is injected after the hole 2 of porous current collector 1, can make active material be uniformly distributed in porous current collector 1, thereby improve embodiment of the present invention Compound Negative electrode capacity.
Certainly, the method that conductive agent, binding agent and active material in above-mentioned steps S01 is dispersed in water-based or oil-based solvent can be also that conductive agent, binding agent and active material are first mixed, then mixture is dispersed in water-based or oil-based solvent, each component is uniformly dispersed, is mixed with emulsion.Can also be that conductive agent, binding agent are added in water-based or oil-based solvent together with active material, then be uniformly dispersed, be mixed with emulsion.
In this step S01, the activated species that conductive agent, binding agent and having embeds lithium ion ability as described above, in order to save length, does not repeat them here.Aqueous solvent is preferably at least one in pure water, deionized water, running water, and oil-based solvent is preferably at least one in 1-METHYLPYRROLIDONE, ethanol, propyl alcohol, cyclohexane.
In above-mentioned steps S02, the mode that above-mentioned slurry injects the hole 2 of porous current collector 1 is preferably one or more combination of cast, deposition, coating, spraying, immersion.This preferred injection mode can be infused in slurry in the hole 2 of porous current collector 1 uniformly, thereby makes so that active material is uniformly distributed in porous current collector 1, thereby improves embodiment of the present invention Compound Negative electrode capacity.Injection rate should make slurry fill to greatest extent the hole 2 of porous current collector 1.
In this step S02, dry treatment process is the slurry drying in the hole 2 in order to make to be coated in porous current collector 1, forms active fillers 3.This dry processing can adopt the drying mode of this area routine, as being dried under vacuum condition, also can in air, dry, air-dry or dry.
In this step S02, in the time that hole collector 1 has more than two, slurry is injected to the hole 2 of every film perforation collector 1, after drying, more dried hole collector 1 is carried out stacked, then through hot pressing, roll or/and sintering processes integrally combines.This hot pressing, roll, method that sintering adopts this area routine.In order to make each stacked porous current collector 1 in conjunction with tightr, porous current collector 1 and active fillers 3 are not caused damage simultaneously, can be according to the selection of porous current collector 1, to hot pressing, roll or/and the condition of sintering processes is adjusted flexibly.
From the above mentioned, the preparation method of the Compound Negative electrode in above-described embodiment only need be mixed with slurry by the active material with embedding lithium ion ability, then be directly injected in the loose structure of collector and be dried, or further dried collector is carried out hot pressing, rolled or/and sintering processes can make this Compound Negative electrode.This preparation method's technique is simple, and condition is easily controlled, and production efficiency is high, has reduced production cost, has effectively avoided existing employing electrodeposition process to produce existing in combination electrode complex process, production efficiency is low, cost is high, the specific energy of battery is low deficiency.
The embodiment of the present invention has also improved a kind of energy high current charge-discharge, takes into account the electrochemical power source of high-energy-density and power.Preferably, above-described embodiment electrochemical power source is preferably the chemical lithium battery of electrochemical reaction or the compound lithium capacitor of electrochemical reaction.Concrete, the chemical lithium battery of this electrochemical reaction is lithium ion battery, lithium polymer battery, lithium-sulfur cell or lithium-air battery; The compound lithium capacitor of electrochemical reaction is lithium-ion capacitor.
As one embodiment of the invention, above-mentioned electrochemical power source is lithium battery, comprise the parts such as housing, electrolyte and battery core, wherein, this battery core comprises the positive electrode/barrier film/negative electrode stacking gradually, the Compound Negative electrode that this negative electricity is very mentioned above, in order to save length, at this, no longer the structure to this Compound Negative electrode and performance repeat.Positive electrode in this lithium battery, barrier film adopt this area to commonly use.Wherein, the structure of this positive electrode also can adopt the structure as Compound Negative electrode in the various embodiments described above, difference is, in the hole of the porous current collector of this positive electrode, be filled with active fillers, this active fillers contains bonding agent, conductive agent and has the positive active material that embeds lithium ion ability.
As another embodiment of the present invention, above-mentioned electrochemical power source is compound lithium capacitor, comprise the parts such as housing, electrolyte and battery core, wherein, this battery core comprises the electrode/barrier film/electrode stacking gradually, this electrode is Compound Negative electrode mentioned above, and in order to save length, at this, no longer the structure to this Compound Negative electrode and performance repeat.This barrier film adopts this area to commonly use.
Above-described embodiment electrochemical power source is owing to containing Compound Negative electrode mentioned above, high just because of this Compound Negative electrode capacity, therefore, has given this electrochemical power source specific energy as high in lithium battery.In addition, above-mentioned Compound Negative electrode volume stability in charge and discharge process, therefore, has given the stable circulation performance of this electrochemical power source excellence, and the cycle life that has extended this electrochemical power source, has strengthened the fail safe of this electrochemical power source.Simultaneously, because the above-mentioned active material in above-mentioned Compound Negative electrode embeds in the loose structure of collector, make the distance of this active material and collector short, shortened electric transmission path short, make this electrochemical power source there is large current density electrical characteristics and high power.
Illustrate above-mentioned Compound Negative electrode and preparation method thereof and lithium battery by multiple embodiment below, with and the aspect such as performance.
A kind of Compound Negative electrode and preparation method thereof:
This Compound Negative electrode structure as shown in Figure 2,3, it comprise nickel foam collector 1 with and mesh 2 in be filled with active fillers 3.The thickness of nickel foam 1 is 150 μ m, and active fillers 3 contains bonding agent, the conductive agent that weight ratio is 8:3:89 and has the active material that embeds lithium ion ability.Wherein, bonding agent is that CMC, conductive agent are SP, and the active material with embedding lithium ion ability is that weight ratio is Si, the SiO of 40:10:50
2nano-powder mixture with graphite.
The method of this Compound Negative electrode:
S11. preparation is containing the slurry of active material: active material powder (active material is not that simple powder mixes, but forms through certain technique sintering, has been finely dispersed compound) is added in pure water, be uniformly dispersed by ultrasonic wave; CMC and SP are dispersed in pure water, are mixed with conducting resinl; The solution that is dispersed with active material is mixed with conducting resinl, be prepared into uniform slurry; Wherein, SP, CMC and active material three weight ratio are 3:8:89, and the concentration of active material in slurry is 35%;
S12. preparation is containing the slurry of active material: by the slurry of nickel foam 1 soaking step S11 preparation, make the upper enough slurries of absorption in the hole of nickel foam, take out and dry, obtain Compound Negative electrode plates.
Compound Negative electrode plates prepared by the present embodiment 1 is for the preparation of poly-lithium battery: Compound Negative electrode plates prepared by the present embodiment 1 and diaphragm material, nickel cobalt lithium aluminate (NCA) anode pole piece are prepared into square polymer battery by winding method.
Embodiment 2
A kind of Compound Negative electrode and preparation method thereof:
As shown in Figure 2,4, it comprises by the two-layer mutually stacked copper mesh collector 11 being combined as a whole and 12 and be filled in the active fillers 3 in the hole 2 of this copper mesh collector 11 and 12 this Compound Negative electrode structure.The thickness of copper mesh collector 11 and 12 is 50 μ m, and active fillers 3 contains bonding agent, the conductive agent that weight ratio is 6:3:91 and has the active material that embeds lithium ion ability.Wherein, bonding agent is that PVDF, conductive agent are VGCF, and the active material with embedding lithium ion ability is nanoscale stannous oxide powder.
The method of this Compound Negative electrode:
S21. preparation contains the slurry of active material: PVDF is added in nmp solvent, be prepared into sol solution, the nano oxidized sub-glass putty body then mixing in advance and the mixture of VGCF conductive agent add in glue body and make uniform slurry; Wherein, PVDF, VGCF and nano oxidized sub-glass putty body three weight ratio are 6:3:91, and the concentration of nano oxidized sub-glass putty body in slurry is 30%;
S22. preparation contains the slurry of active material: the slurry of step S21 preparation is poured in the hole 2 of two copper mesh collectors 11,12, dry, make two single-layer electrodes pole pieces, then by stacked two single-layer electrodes pole pieces, through 150 ℃ of high temperature hot pressings, two stacked single-layer electrodes pole pieces are combined into one, obtain Compound Negative electrode plates.
Compound Negative electrode plates prepared by the present embodiment 2 is for the preparation of poly-lithium battery: Compound Negative electrode plates prepared by the present embodiment 2 cuts into small pieces, is prepared into square flexible-packed battery with diaphragm material, the little pole piece of nickle cobalt lithium manganate tertiary cathode by Z-type lamination mode.
Embodiment 3
A kind of Compound Negative electrode and preparation method thereof:
This Compound Negative electrode structure is as shown in Fig. 2,5, and it comprises by three layers of mutual stacked stainless (steel) wire collector being combined as a whole 11,12 and 13 and is filled in the active fillers 3 in the hole 2 of this stainless (steel) wire collector 11,12 and 13.The thickness of stainless (steel) wire collector 11,12 and 13 is 40 μ m, and active fillers 3 contains bonding agent, the conductive agent that weight ratio is 6:2:92 and has the active material that embeds lithium ion ability.Wherein, bonding agent is that CMC+SBR (weight ratio 1:1), conductive agent are CNTs, and the active material with embedding lithium ion ability is nano silicone carbon complex powder (in compound, the content of Si is 40%).
The method of this Compound Negative electrode:
S31. preparation contains the slurry of active material: SP is added in CMC+SBR solvent, be prepared into conducting resinl, then nano silicone powder added in conducting resinl and make uniform slurry; Wherein, CMC+SBR, CNTs and nano silicone carbon complex three weight ratio are 6:2:92, and the concentration of nano silicone carbon complex in slurry is 42%;
S32. preparation contains the slurry of active material: the slurry of step S31 preparation is poured in the hole 2 of three stainless (steel) wire collectors 11,12 and 13, dry, make three single-layer electrodes pole pieces, then by stacked three single-layer electrodes pole pieces, hot pressing at 120 ℃, make three stacked single-layer electrodes pole pieces be pressed into one, obtain Compound Negative electrode plates.
Compound Negative electrode plates prepared by the present embodiment 3 is for the preparation of poly-lithium battery: Compound Negative electrode plates prepared by the present embodiment 3 and diaphragm material, lithium cobaltate cathode pole piece are prepared into square aluminum housing battery by winding method.
Lithium battery performance test:
Carry out multiplying power discharging property and cycle performance test according to above-described embodiment 1 to embodiment 3 with take existing lithium battery (battery size 454261P) as comparison example, this multiplying power discharging property and cycle performance test are according to method test well known in the art.The results are shown in shown in table 1.Wherein, as shown in Figure 7, multiplying power discharging property test is as shown in table 1 below for cycle performance test result:
Table 1
As shown in Table 1, the lithium ion battery that uses the prepared Compound Negative electrode of the present invention to prepare, has higher capacity, has improved more than 20% than the capacity of conventional graphite electrode; And there is the lithium ion battery forming than the graphite electrode of conventional structure and there is better high rate performance.
As shown in Figure 7, the lithium ion battery that uses the prepared Compound Negative electrode of the present invention to prepare, have than cyclical stability preferably, after 200 circulations, capability retention is still greater than more than 75%, if be converted into capacity, after 200 circulations, its discharge capability is all better than the lithium ion battery that graphite electrode forms.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (15)
1. a Compound Negative electrode, comprise the porous current collector of one deck or two-layer above stacked combination, in the hole of described porous current collector, be filled with active fillers, described active fillers contains bonding agent, conductive agent and has the active material that embeds lithium ion ability, and it is 80～98% that described active material accounts for described active fillers total weight percent.
2. Compound Negative electrode as claimed in claim 1, is characterized in that, described active material is at least one in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle of M element, or
Described active material is at least one and the compound of carbon in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle of M element;
Wherein, described M element is at least one in Si, Sn, Al, Sb, Ge, Zn, Pb, Mg, Na.
3. Compound Negative electrode as claimed in claim 2, it is characterized in that, in at least one in the nano simple substance particle of described M element, nano wire, nanotube, nanofiber, nano thin-film, nano-oxide particles, Nanoalloy particle and the compound of carbon, the weight content of described M element activity material in described compound is 10 ~ 98%.
4. Compound Negative electrode as claimed in claim 2 or claim 3, is characterized in that, the particle diameter of described nano simple substance particle, nano-oxide particles or Nanoalloy particle is 1～800nm.
5. Compound Negative electrode as claimed in claim 1, is characterized in that, the number of plies of described porous current collector is 1～20 layer.
6. the Compound Negative electrode as described in claim 1 or 5, is characterized in that, described porous current collector is nickel foam, foam copper, foamed aluminium, foamy carbon, Stainless Steel net, nickel screen, copper mesh or aluminium net.
7. the preparation method of the Compound Negative electrode as described in as arbitrary in claim 1～6, comprises the steps:
By described conductive agent, binding agent and described in there is the active material that embeds lithium ion ability and be dispersed in water-based or oil-based solvent, preparation is containing the slurry of active material; Wherein, the weight ratio of described active material, conductive agent, binding agent is 100:(0～15): (1～15), the content of described active material in described slurry is 20%～70%;
Described slurry is injected to the hole of a slice porous current collector, dry, obtain described Compound Negative electrode; Or
Described slurry is injected to the hole of at least two porous current collectors, dry, then by dried described porous current collector carry out stacked and through hot pressing, roll or/and sintering processes integrally combines, obtain described Compound Negative electrode.
8. the preparation method of Compound Negative electrode as claimed in claim 7, is characterized in that, the mode that described slurry is injected to the hole of porous current collector is cast, deposition, apply, spraying, soak, one or more combination of printing.
9. the preparation method of Compound Negative electrode as claimed in claim 7, is characterized in that, described aqueous solvent is at least one in pure water, distilled water, running water;
Described oil-based solvent is at least one in 1-METHYLPYRROLIDONE, ethanol, propyl alcohol, cyclohexane.
10. an electrochemical power source, comprises the arbitrary described Compound Negative electrode of claim 1～6.
11. electrochemical power sources as claimed in claim 10, is characterized in that, the compound lithium capacitor of the chemical lithium battery that described electrochemical power source is electrochemical reaction or electrochemical reaction.
12. electrochemical power sources as claimed in claim 11, is characterized in that, the chemical lithium battery of described electrochemical reaction is liquid lithium ion battery, lithium polymer battery, lithium-sulfur cell or lithium-air battery.
The preparation method of 13. Compound Negative electrodes as claimed in claim 11, is characterized in that, described compound lithium capacitor is lithium-ion capacitor.
The application of 14. electrochemical power sources as described in claim 10～13 any one in mobile terminal product, electric automobile, electrical network, communication equipment and/or electric tool.
The application of 15. electrochemical power sources as claimed in claim 14, is characterized in that: described communication equipment comprises operational module and supply module, and described supply module comprises described electrochemical power source, the chemical lithium battery that described electrochemical power source is electrochemical reaction; Described supply module provides electric energy for described operational module, the electric energy operation that described operational module uses described supply module to provide.
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