CN103794767A - Lithium battery cathode material, cathode, lithium battery, preparation method and communication equipment thereof - Google Patents
Lithium battery cathode material, cathode, lithium battery, preparation method and communication equipment thereof Download PDFInfo
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- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a lithium battery cathode material and a preparation method thereof, a lithium battery cathode and a preparation method thereof, a lithium battery and a preparation method thereof, and communication equipment. The lithium battery cathode material comprises a nano-material able to undergo alloying with lithium, an organic group bonded to the surface of the nano-material and a metal particle adsorbed on the organic group, wherein the nano-material and the metal particle are in electrical connection through the organic group. The lithium battery cathode, the lithium battery and the communication equipment all contain the lithium battery cathode material. The lithium battery cathode material has the advantages of stable volume and structure, and strong conductivity, so that the lithium battery can have stable electrochemical performance in charge-discharge cycles, high capacity, and long life.
Description
Technical field
The invention belongs to battery technology field, be specifically related to a kind of lithium cell cathode material and preparation method thereof, cathode of lithium battery and preparation method thereof, lithium battery and preparation method thereof and communication equipment.
Background technology
At present, along with growing to high power capacity, long-life batteries demand of mobile electronic equipment, people have higher requirement to the performance of lithium ion battery.Capacity of lithium ion battery is on the low side has become a bottleneck of restriction battery industry development.Therefore, find the positive electrode of height ratio capacity more and negative material and become a developing direction in battery material field.Negative material is the important component part of lithium ion battery, and it is restricting the commercialization process of lithium ion battery, and meanwhile, the development of portable cell and high power capacity electrokinetic cell, has also strengthened the demand for high-energy, high cycle performance negative material.
Along with people are for the continuous exploration of negative material, the material that can form alloy with lithium becomes the most promising class negative material in high-performance lithium ion battery because of its higher theoretical capacity, good embedding/deviate from ability, for example the theoretical capacity of pure silicon material, up to 4200mAh/g, is approximately ten times of graphite cathode.But the cyclical stability of this type of material is poor, cycle life is shorter, and main cause is in charge and discharge cycles process, and huge volumetric expansion, contraction can occur material, if the cubical expansivity of silicon is 300%.Can cause again thus the destruction of conductive network, further worsen the chemical property of material.Below by represent with A above-mentioned can with the negative material of lithium alloyage.
In order to address the above problem, industry mainly adopts nanometer, filming, Composite and designs four kinds of modes of multistage special construction it is carried out to modification at present, and all kinds of improvement concrete grammars are as follows:
1. nanometer:
For solving huge volumetric expansion, the contraction problem of A material, industry generally acknowledges that by its nanometer processing be a kind of effectively solution route.Main cause is for reducing 1/2 when particle diameter, and volume is corresponding reduces 1/8.People adopt respectively high-energy ball milling method, laser method, high-temperature calcination, sol-gel process etc. to prepare nano-powder; Adopt gas-liquid-solid (VLS) growth method, Fabricated by Oxide-assisted Growth Mechanism method, plasma activation method, electrodeposition process etc. to prepare nano wire and nanotube.
But also existent defect of this existing method for making Nano: the dimension that reduces material does not fundamentally solve the problem of the intrinsic volumetric expansion of material, contraction and poorly conductive, and effectively size is difficult to realize as nano particle diameter <10nm.The high surface energy of nano particle also can lure that serious agglomeration occurs storeroom into simultaneously, finally causes battery performance not fully up to expectations.The preparation cost of nanowires/nanotubes is high, the production cycle is long, and nanowire length is limited, is difficult to practical.
2. filming:
Thin-film material has larger specific area, by material filmization can effectively reduce with film vertical direction on the change in volume that produces, thereby improve the cyclical stability of material.Therefore thin-film material generally has high specific capacity and good cycle performance.
But also existent defect of this existing filming method: current thin filmization mainly adopts the methods such as chemical vapour deposition technique, magnetron sputtering method, pulsed laser deposition, vacuum evaporatation to prepare thin-film material, its complicated process of preparation, cost is higher, be difficult to rapid large-scale and produce, commercialization process is limited.And the specific area that film is larger causes side reaction and irreversible capacity to increase.
3. Composite:
Main introduce good conductivity, active or nonactive buffering matrix that bulk effect is little by means such as coated, doping, prepare heterogeneous composite negative pole material, thereby suppress and volumetric expansion, the contraction of lithium alloyage negative material.It roughly can be divided into the nonmetal compound system of (1) A-(being mainly A/ carbon complex system); (2) two kinds of systems of A-metal composite system.
But also existent defect of this existing Composite method: A/ metal alloy system can be improved the electric conductivity of A material, but still has breakage of particles and pulverizing problem, limits it and further develops; In A/ carbon composite, carbon occupies larger proportion conventionally, and the content of A is less, therefore weakened the high power capacity advantage of this material.
From the above, no matter adopt above-mentioned which kind of existing method, its effect is all undesirable, or preparation process complexity, is difficult to realize commercialization, or the introducing of a large amount of inert matters has greatly weakened the advantage of A material high power capacity.
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, lithium cell cathode material that conductivity is high and preparation method thereof.
Another object of the embodiment of the present invention is to provide a kind of cathode of lithium battery that contains this lithium cell cathode material and preparation method thereof.
The another object of the embodiment of the present invention is to provide a kind of lithium battery that contains this cathode of lithium battery and preparation method thereof.
An object again of the embodiment of the present invention is to provide a kind of communication equipment that contains this lithium battery.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of lithium cell cathode material, comprises
Can with the nano material of lithium alloyage; With
Be bonded in the organic group of described nano-material surface; And
Be adsorbed on the metallic on described organic group;
Wherein, described nano material and metallic electrically connect by described organic group.
Preferably, the general formula of above-mentioned organic group is-(CH
2) n-B-R, 0≤n≤100 in general formula, B is at least one in aliphat, aromatic series, heterocyclic group, R is at least one in benzoxy, phenylacetic acid base, benzene sulfonic acid base.
Preferably, above-mentioned metallic is at least one in Ag, Au, Pt, Mn, Mo, Nb, W, Ta, Fe, Cu, Ti, V, Cr, Ni, Co, Zr, Y metallic.
Preferably, above-mentioned nano material is at least one in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, Nanoalloy particle of M element; Wherein, described M element is at least one in Si, Sn, Ge, Pb, Sb, Al, Zn.
Particularly, above-mentioned nano simple substance particle is or/and the particle diameter of Nanoalloy particle is 50～200nm.
Preferably, above-mentioned metallic accounts for 2～10% of described lithium cell cathode material gross mass.
Preferably, above-mentioned organic group accounts for 2～8% of described lithium cell cathode material gross mass.
And a kind of preparation method of above-mentioned lithium cell cathode material, comprises the steps:
By described can be with the nano material of lithium alloyage, contain the bonding organic substance at described nano-material surface organic group, the first organic solvent mixes, stirring reaction or ball milling carry out Separation of Solid and Liquid, collecting precipitation after 6～20 hours;
After described precipitation is dry, add in polar solvent, add slaine, stir and add reducing agent after 0.5～4 hour, make the metal ion generation redox reaction in itself and described slaine, after 6～20 hours, carry out Separation of Solid and Liquid, purifying, obtains described lithium cell cathode material.
Further preferably, by above-mentioned can with the nano material of lithium alloyage with contain before the bonding organic substance at described nano-material surface organic group, the first organic solvent mix, also comprise described nano material carried out to pretreated step:
By described nano material and HF or NH
4f solution mix and blend reacts, and removes the oxide layer of described nano-material surface.
Preferably, the mass ratio of above-mentioned nano material and organic substance consumption is 4:1～10:1.
Preferably, above-mentioned organic substance is at least one in primary amine or its mixture of 3,4,5-trifluoromethyl aniline, p-aminobenzoic acid, equal amido phenenyl acid, sulfanilic acid and aliphat, aromatic series and heterocycle.
Preferably, above-mentioned the first organic solvent is at least one in acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, formic acid, acetic acid, pentane, hexane, octane.
Preferably, the mass ratio of above-mentioned precipitation, slaine and reducing agent consumption is 4:1:1～10:1:1.
Preferably, above-mentioned slaine is at least one soluble-salt in Ag salt, Au salt, Pt salt, Mn salt, Mo salt, Nb salt, W salt, Ta salt, Fe salt, Cu salt, Ti salt, V salt, Cr salt, Ni salt, Co salt, Zr salt, Y salt.
Preferably, above-mentioned reducing agent is hydrazine, NaBH
4, at least one in sodium thiosulfate, iron ammonium sulfate, vulcanized sodium.
And a kind of cathode of lithium battery, comprises collector and is combined in the negative material that contains on described collector, described negative material is above-mentioned lithium cell cathode material.
And a kind of cathode of lithium battery preparation method, comprises the steps:
By above-mentioned lithium cell cathode material and electrodes conduct agent, bonding agent and, solvent, and be mixed with cathode size;
Described cathode size is coated on collector;
The described collector that is coated with cathode size is dried to processing, roll-in, cutting, obtains cathode of lithium battery.
Preferably, the weight ratio of above-mentioned lithium cell cathode material, electrodes conduct agent, bonding agent and solvent is 6:(1.5 ~ 3.5): (1.5 ~ 3.5): (90 ~ 100).
And, a kind of lithium battery, described lithium battery comprises the cathode of lithium battery that power is above-mentioned.
Preferably, above-mentioned lithium battery is that lithium ion battery is or/and lithium polymer battery.
And a kind of lithium battery preparation method, comprises the steps:
Prepare lithium battery anode and negative pole, described cathode of lithium battery is prepared from by above-mentioned cathode of lithium battery preparation method;
Described lithium battery anode, barrier film, described cathode of lithium battery are stacked gradually, and reel, make battery battery core;
Described battery core is packed in battery container, the electrolyte that reinjects, sealing, makes lithium battery.
The embodiment of the invention also discloses a kind of communication equipment, this communication equipment comprises operational module and supply module, and described supply module comprises above-mentioned lithium battery; 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-described embodiment lithium cell cathode material, take can be with the nano material of lithium alloyage as core, adopts organic group for buffering skeleton, makes this lithium cell cathode material volume stability.The metallic adsorbing on this organic group, by the charge transfer of this organic group, realizes metallic and this nano material electrically connecting between the two, has effectively strengthened the electric conductivity of this lithium cell cathode material.Simultaneously, by the absorption of this organic group, this metallic can evenly and be firmly distributed in around nano material, improve the stability of lithium cell cathode material structure, make to keep better electrically connecting between nano material and metallic, reduce to occur disconnecting in electrical conductivity network, improve the chemical property of lithium cell cathode material.
The preparation method of above-described embodiment lithium cell cathode material adopts ball-milling method or organic chemical reactions to be prepared from conjunction with redox reaction, each technology maturation, condition is easily controlled, production efficiency is high, reduce production cost, effectively avoided existing negative material complicated process of preparation, production efficiency is low, cost is high deficiency.
Above-described embodiment cathode of lithium battery is owing to containing above-mentioned lithium cell cathode material, again because this lithium cell cathode material has volume as above and Stability Analysis of Structures, the advantage that conductivity is high, therefore, the stable performance in the course of the work of this negative pole, conductivity is high, stabilized structure, avoid because of the violent expansion of active material volume, the obscission that contraction causes, effectively extended cathode of lithium battery useful life.This cathode of lithium battery preparation method technology maturation, qualification rate is high.
Above-described embodiment lithium battery is owing to containing above-mentioned cathode of lithium battery, this lithium battery stable electrochemical property in charge and discharge cycles process, and capacity is high, and the life-span is long.This lithium battery preparation method technology maturation, qualification rate is high.
When this lithium battery is used for to the supply module of above-described embodiment communication equipment, the supply module of this communication equipment can be to operational module stable and continue electric energy is provided, reduce the replacement frequency to battery in supply module, reduced the cost of this communication equipment operation.
Preparation method's technique of lithium cell cathode material, lithium battery anode and lithium battery in above-described embodiment is simple, and condition is easily controlled, and efficiency is high, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is a kind of structural representation of embodiment of the present invention lithium cell cathode material;
Fig. 2 is the another kind of structural representation of embodiment of the present invention lithium cell cathode material;
Fig. 3 is preparation method's flow chart of embodiment of the present invention lithium cell cathode material;
Fig. 4 is preparation method's flow chart of embodiment of the present invention cathode of lithium battery;
Fig. 5 is preparation method's flow chart of embodiment of the present invention lithium battery;
Fig. 6 is first three charging and discharging curve figure of lithium ion battery prepared by the embodiment of the present invention 1;
Fig. 7 is cycle performance of lithium ion battery curve chart prepared by the embodiment of the present invention 1,2,3 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 volume stability, the lithium cell cathode material that conductivity is high, and its structure is referring to as shown in Figure 1, Figure 2.This lithium cell cathode material comprises can be with the nano material of lithium alloyage 1, be bonded in the organic group 2 on this nano material 1 surface and be adsorbed on the metallic 3 on this organic group 2.Wherein, this nano material 1 is touched by organic group 2 Electricity Federations with metallic 3.
Particularly, above-mentioned nano material 1 is preferably at least one in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, Nanoalloy particle of M element; Wherein, described M element is at least one in Si, Sn, Ge, Pb, Sb, Al, Zn.This preferred nano material 1 has high capacity, gives above-described embodiment lithium cell cathode material high capacity characteristics.Due to the difference of nano material 1 selection, will directly cause the difference of above-described embodiment lithium cell cathode material structure, have particularly several examples at least:
One embodiment, nano material 1 is nano simple substance particle and/or Nanoalloy particle, organic group 2 is bonded in the surface of nano material 1 uniformly, metallic 3 is adsorbed on this organic group 2, like this, this metallic 3 is evenly distributed in nano material 1 around, and making this lithium cell cathode material microstructure is spherical or almost spherical, and its structure as shown in Figure 1.
Another embodiment, nano material 1 is at least one in nano wire, nanotube, nanofiber, organic group 2 is bonded in the surface of nano material 1 uniformly, metallic 3 is adsorbed on this organic group 2, like this, this metallic 3 is evenly distributed in nano material 1 around, make this lithium cell cathode material microstructure with nano wire, nanotube or/and the microstructure of nanofiber is close, figure is slightly.
An embodiment again, nano material 1 is nano thin-film, organic group 2 is bonded in the surface of nano material 1 uniformly, metallic 3 is adsorbed on this organic group 2, like this, this metallic 3 is evenly distributed in receives nano thin-film surface, and making this lithium cell cathode material microstructure is membrane structure, and its structure as shown in Figure 2.
Further, inventor also finds under study for action, and the particle size of above-mentioned nano material 1 is controlled to certain limit, can further improve the specific capacity of this lithium cell cathode material.In a preferred embodiment, in the time that nano material 1 is selected from least one in nano simple substance particle and/or Nanoalloy particle, this nano simple substance particle is or/and the particle diameter of Nanoalloy particle is 50～200nm.In the time that nano material 1 is selected from least one in nano wire, nanotube, nanofiber, nano thin-film, this nano wire, nanotube, nanofiber, nano thin-film all can be selected the model of this area routine.
Above-mentioned organic group 2 is preferably selected from general formula
2) organic group of n-B-R, 0≤n≤100 in general formula, B is at least one in aliphat, aromatic series, heterocyclic group, R is at least one in benzoxy, phenylacetic acid base, benzene sulfonic acid base.This preferred organic group 2 on the one hand can be by a series of Proton-Transfer Reactions well and the surperficial generation bonding of HF nano material 1 after treatment; On the other hand owing to containing electronegative R group, can effectively by the absorption of electric charge, metallic 3 be adsorbed on this organic group 2, strengthen the stability of this lithium cell cathode material structure, simultaneously, also, due to the absorption of organic group 2 to metallic 3, make this metallic 3 can more be evenly distributed in nano material 1 surface.As preferred embodiment, the quality percentage composition of this organic group 2 in this lithium cell cathode material is 2～8%.This content range organic group 2, can better build buffering skeleton, further improve this lithium cell cathode material volume stability, can also adsorb the metallic 3 of respective amount simultaneously, and this metallic 3 can be distributed at nano material 1 surface uniform, improve the electric conductivity of this lithium cell cathode material.Certainly, in embodiments of the present invention, if do not consider structural stability and the conductivity of this lithium cell cathode material excellence, this organic group 2 can also select can with other organic groups of nano material 1 surface bond and adsorbing metal particles 3 functions.
Above-mentioned metallic 3, in above-described embodiment lithium cell cathode material, is with metal simple-substance or/and the small crystal form of metal exists, and by and above-mentioned organic group 2 between electric charge absorption be distributed in organic group 2.As preferred embodiment, this metallic 3 is selected from least one in Ag, Au, Pt, Mn, Mo, Nb, W, Ta, Fe, Cu, Ti, V, Cr, Ni, Co, Zr, Y metallic.This preferred metallic 3 can better and above-mentioned organic group 2 between electric charge absorption, more firm with organic group 2 combinations, thus improved the stability of above-described embodiment lithium cell cathode material structure.Due in this lithium cell cathode material, this metallic 3 plays the effect that strengthens conductive effect again, and therefore, this metallic 3 can also be selected other metallics with electric conductivity.
Further, inventor finds after deliberation, in above-described embodiment lithium cell cathode material, and this lithium cell cathode material electric conductivity of the content influence of this metallic 3.Therefore,, in order to make this lithium cell cathode material have excellent electric conductivity and relatively low cost, in a preferred embodiment, the quality percentage composition of this metallic 3 in this lithium cell cathode material is 2～10%.Certainly,, if ignore quality and the Cost Problems of the electric conductivity of material, these metallic 3 content can also, below or above this content range, can be realized the embodiment of the present invention.
From the above, above-described embodiment lithium cell cathode material is take can be with the nano material of lithium alloyage 1 as core, adopt organic group 2 for buffering skeleton, make this lithium cell cathode material volume stability, effectively alleviated the deficiency of the volumetric expansion in charge and discharge cycles process in the prior art.The metallic 3 of absorption on this organic group 2, by the charge transfer of this organic group 2, realizes metallic 3 and this nano material 1 electrically connecting between the two, has effectively strengthened the electric conductivity of this lithium cell cathode material.Simultaneously, by the absorption of this organic group 2, this metallic 3 can evenly and be firmly distributed in around nano material 1, improve the stability of lithium cell cathode material structure, make to keep better electrically connecting between nano material 1 and metallic 3, reduce to occur disconnecting in electrical conductivity network, improve the chemical property of lithium cell cathode material.Compared with the A-metal composite system (referring to background technology) of preparing with existing Composite, what this metallic 3 more can homogeneous is distributed in nano material 1 surface, has effectively avoided breakage of particles and pulverizing problem.
Correspondingly, the embodiment of the present invention also provides a kind of preparation method of above-mentioned lithium cell cathode material, and this Compound Negative electrode preparation method technological process refers to Fig. 3.This lithium cell cathode material is preparation method comprise the steps:
Step S01. is at nano-material surface bonding organic group: can be with the nano material of lithium alloyage, contain the bonding organic substance at this nano-material surface organic group, the first organic solvent mixes, stirring reaction or ball milling carry out Separation of Solid and Liquid, collecting precipitation after 6～20 hours;
Step S02. is adsorbing metal particles on organic group by Electrostatic Absorption and redox: the precipitation that step S01 is collected adds in polar solvent after being dried, add slaine, stir and add reducing agent after 0.5～4 hour, make the metal ion generation redox reaction in itself and described slaine, after 6～20 hours, carry out Separation of Solid and Liquid, purifying, obtains described lithium cell cathode material.
Particularly, not can, with the nano material of lithium alloyage as the nano material 1 described in above-described embodiment lithium cell cathode material, in order to save length, not repeat them here in above-mentioned steps S01.
This contains the bonding organic substance at described nano-material surface organic group and is selected from the organic substance that contains above-mentioned organic group 2, and wherein, this organic substance is preferably selected from and contains general formula for-(CH
2) organic substance of n-B-R group, 0≤n≤100 in general formula, B is at least one in aliphat, aromatic series, heterocyclic group, R is at least one in benzoxy, phenylacetic acid base, benzene sulfonic acid base.Concrete, this organic substance is at least one in primary amine or its mixture of 3,4,5-trifluoromethyl aniline, p-aminobenzoic acid, equal amido phenenyl acid, sulfanilic acid and aliphat, aromatic series and heterocycle.Certainly, if do not consider the structural stability of this lithium cell cathode material and good conductivity, this organic group can also select contain can with the organic substance of other organic groups well known in the art of above-mentioned nano material 1 surface bond and adsorbing metal particles 3 functions.
This first organic solvent is preferably selected from least one in acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, formic acid, acetic acid, pentane, hexane, octane.Certainly, this organic molten can also selecting can be dissolved above-mentioned organic other organic solvents, is not particularly limited in embodiments of the present invention.
As the preferred embodiment of the present invention, the nano material in above-mentioned steps S01 and organic amount ratio are 4:1～10:1 (mass ratio); The consumption of the first organic solvent should be enough, if the amount ratio of the consumption of the first organic solvent and nano material is 80:1～200:1 (mass ratio).
In this step S01, above-mentioned nano material, organic substance and the first organic solvent carry out stirring reaction or ball-milling treatment after mixing, and make this organic substance and nano-material surface generation bonding, and this organic functional group is bonded in to this nano-material surface.Wherein, the temperature of stirring reaction or ball-milling treatment does not have special requirement, can be all to carry out under the condition of normal temperature or room temperature, and ball-milling treatment can directly adopt the conventional ball milling condition in this area.The principle of stirring reaction bonding is based on diazo-reaction, and detailed process is with reference to chemical schematic diagram below (take the reaction of Si as example):
The principle of ball-milling treatment bonding is mainly based on mechanochemical treatment principle, in level of chemical reaction, mainly refer to by means such as shearing, friction, impact, extruding, the condensed state matter such as solid, liquid is applied to mechanical energy, induce its structure and physicochemical properties to change, and induced chemical reaction.
As the preferred embodiment of the present invention; the nano simple substance particle that is selected from M element when above-mentioned nano material is or/and Nanoalloy particle; wherein; when described M element is at least one in Si, Sn, Ge, Pb, Sb, Al, Zn, above-mentioned nano material and organic bonding method can be selected stirring reaction bonding or ball-milling treatment bonding flexibly.Certainly,, if also have additive method known in this field can make both that bonding occurs, also can adopt other bonding method.
Or as the preferred embodiment of the present invention, the nano wire, nanotube, nanofiber that are selected from M element when above-mentioned nano material are or/and nano thin-film, wherein, when described M element is at least one in Si, Sn, Ge, Pb, Sb, Al, Zn, above-mentioned nano material and organic bonding method adopt stirring reaction bonding.Like this, guarantee to greatest extent the integrality of this nanometer material structure, avoided the destruction of ball milling bonding method to this nanometer material structure.Certainly,, if ignore the integrality to this nanometer material structure, also can adopt in a preferred embodiment the method for ball milling bonding by both bondings.
In this step S01, the mode of Separation of Solid and Liquid can adopt suction filtration, collects filter cake, i.e. product after above-mentioned nano material and organic bonding.Certainly, can also adopt other modes well known in the art to realize Separation of Solid and Liquid, obtain filter cake.In order to remove organic solvent or the organic substance of bonding not to occur, obtain pure product, preferably filter cake is carried out to purification process, the mode of this purification process can be: adopt absolute ethyl alcohol to clean filter cake until filtrate is colourless.
Further, as the preferred embodiment of the present invention, by above-mentioned can with the nano material of lithium alloyage with contain before the bonding organic substance at this nano-material surface organic group, the first organic solvent mix, also comprise described nano material is carried out to pretreated step, these preliminary treatment concrete steps are as follows:
By this nano material and HF or NH
4f solution mix and blend reacts, and removes the oxide layer of described nano-material surface.Wherein, nano material and HF or NH
4f solution usage is than (3～15) g:1ml, nano material and HF or NH
4the time of F stirring reaction is 5～30min, HF or NH
4f solution can be 4%～8% (mass fraction).
Because some raw material of nano material can form one deck oxide on surface, by this preliminary treatment, oxide is removed, effectively improve this nano material and the organic substance generation bonding that contains above-mentioned organic group.
In above-mentioned steps S02, after slaine adds, in the process stirring, adsorb by the electric charge being bonded between the metal ion in organic group and the slaine of above-mentioned nano-material surface, by adsorption of metal ions on this organic group.After adding reducing agent, this reducing agent and this metal ion generation redox reaction, be reduced into metallic atom by this metal ion.Form little crystal grain because adjacent metal atom can occur to reunite, therefore, the little crystal grain of metal after metallic atom and/or part are reunited is adsorbed on organic group, jointly forms as the metallic 3 in Fig. 1,2.
Electric charge adsorption process and redox reaction process in this step S02 all do not have special requirement to the factor such as temperature, pressure, as can be all carries out under the condition of normal temperature or room temperature and normal pressure.Certainly,, for accelerated charge adsorption and oxidation reduction reaction, electric charge adsorption process and redox reaction process are all preferably attended by agitating procedure.
Wherein, to be preferably selected from described slaine be at least one the soluble-salt in Ag salt, Au salt, Pt salt, Mn salt, Mo salt, Nb salt, W salt, Ta salt, Fe salt, Cu salt, Ti salt, V salt, Cr salt, Ni salt, Co salt, Zr salt, Y salt to above-mentioned slaine.Certainly, in embodiments of the present invention, can also adopt well known in the art and can be reduced agent and be reduced into other soluble metallic salts of elemental metals.
Particularly, this Ag salt can be AgNO
3, at least one in AgCOOH, Au salt can be AuCl
3, Pt salt can be PtCl
2, Mn salt can be MnCl
2, MnSO
4h
2at least one in O, Mo salt can be MoCl
5, Nb salt can be NbF
5, W salt can be WOCl
4, Ta salt can be Ta (OH)
5, Fe salt can be FeCl
2, Cu salt can be Cu (NO
3)
2, CuCl
2in at least one, Ti salt can be Ti (SO
4)
29H
2o, V salt can be VOSO
45H
2o, Cr salt can be Cr
2(SO
4)
3, Ni salt can be NiSO
46H
2o, Co salt can be CoCl26H
2o, Zr salt can be ZrCl
4.
Above-mentioned reducing agent is preferably selected from hydrazine (NH
2-NH
2), sodium borohydride (NaBH
4), sodium thiosulfate (Na
2s
2o
3), iron ammonium sulfate [(NH
4)
2fe (SO
4)
2], vulcanized sodium (Na
2s) at least one in.
Above-mentioned polar solvent is preferably selected from C
2h
3n, H
2o, CH
3oH, C
2h
5oH, C
3h
7alcohols such as OH and composition thereof.This preferred polar solvent can be conducive to slaine and ionize out metal ion.
Certainly, this is organic moltenly can also select other organic solvents that can dissolve above-mentioned reducing agent, is not particularly limited in embodiments of the present invention.
As the preferred embodiment of the present invention, the amount ratio of precipitation, slaine and reducing agent in above-mentioned steps S02 is 4:1:1～10:1:1(mass ratio).The consumption of polar solvent should be enough, if the amount ratio of the consumption of polar solvent and precipitation is 80:1～200:1 (mass ratio).
From the above mentioned, the preparation method of above-mentioned lithium cell cathode material, by by nano material, the organic substance bonding that contains organic group, is then prepared from by the reduction of electric charge adsorption and oxidation.This preparation method's technique is simple, and condition is easily controlled, and production efficiency is high, and production cost is low.
The present invention further provides a kind of cathode of lithium battery, and it comprises collector and be combined in the negative material that contains on this collector, and wherein, this negative material is lithium cell cathode material mentioned above; Collector can be selected the conventional collector in this area, as Copper Foil etc.Like this, this cathode of lithium battery is owing to containing lithium cell cathode material mentioned above, again because this lithium cell cathode material has volume as above and Stability Analysis of Structures, conductivity is high, therefore, and the stable performance in the course of the work of this negative pole, conductivity is high, stabilized structure, has avoided because obscission occurs for violent expansion, the contraction of active material volume, has effectively extended cathode of lithium battery useful life.This cathode of lithium battery preparation method technology maturation, qualification rate is high.
Correspondingly, the present invention further provides above-mentioned cathode of lithium battery preparation method.This lithium battery anode preparation method technological process refers to Fig. 4, and it comprises the steps:
Step S03. prepares cathode size: by lithium cell cathode material mentioned above and electrodes conduct agent, bonding agent, solvent and be mixed with cathode size;
Step S04. is coated in the cathode size of step S03 preparation on collector;
Dry, the roll-in of step S05. collector and cutting processing: the collector that is coated with cathode size of processing through step S04 is dried to processing, roll-in, cutting, obtains cathode of lithium battery.
Particularly, the weight ratio of the lithium cell cathode material in above-mentioned steps S03, electrodes conduct agent, bonding agent and solvent is preferably 6:(1.5 ~ 3.5): (1.5 ~ 3.5): (90 ~ 100), more preferably 6:2:2:100.Above-mentioned electrodes conduct agent is at least one in graphite, acetylene black, SP, KS-6, Single Walled Carbon Nanotube, multi-walled carbon nano-tubes; Described bonding agent is at least one in sodium carboxymethylcellulose (CMC), SBR, WSB, LiPAA, PI; Solvent is preferably water.Certainly, this electrodes conduct agent, bonding agent, solvent can also be selected other conventional materials of this area.
In above-mentioned steps S04, apply the mode of cathode size and mode that step S05 is dried processing, roll-in, cutting to collector and all can adopt the conventional method in this area.
This cathode of lithium battery preparation method only need be coated in the cathode size that contains lithium cell cathode material mentioned above on collector, then drying, roll-in, cutting process, and the method is simple, and condition is easily controlled, and qualification rate and production efficiency are high.
Example of the present invention also provides a kind of lithium battery, and this lithium battery comprises cathode of lithium battery mentioned above.
As preferred embodiment, this lithium battery is the chemical lithium battery of the electrochemical reactions such as lithium ion battery, lithium polymer battery.
Like this, this lithium battery is owing to containing cathode of lithium battery mentioned above, this lithium battery stable electrochemical property in charge and discharge cycles process, and capacity is high, and the life-span is long.
Correspondingly, the embodiment of the present invention further provides a kind of above-mentioned lithium battery preparation method.This lithium battery preparation method technological process refers to Fig. 5, and it comprises the steps: 2
Step S06. prepares lithium battery anode and negative pole, and wherein, this cathode of lithium battery is cathode of lithium battery preparation method be by mentioned earlier prepared from;
Step S07. prepares battery battery core: step S06 is prepared to anode and negative pole and stack gradually according to the negative overlapped way of lithium battery anode/barrier film/lithium battery, and reel, make battery battery core;
Step S08. packaged battery: described battery core is packed in battery container, the electrolyte that reinjects, sealing, makes lithium battery.
Particularly, in above-mentioned steps S06, the packaged battery method in preparation and the step S08 of the battery battery core in preparation, the step S07 of positive pole all can be according to the method preparation of this area routine.Wherein the battery battery core in step S07 can square or other shapes that need according to different lithium battery.Like this, preparation method's technology maturation of this lithium battery, condition is easily controlled, and qualification rate is high.
In addition, the embodiment of the present invention also provides a kind of communication equipment, and this communication equipment comprises operational module and supply module.Wherein, supply module provides electric energy for operational module, and it comprises lithium battery mentioned above, and this lithium battery can be one or more lithium battery.When putting supply module and comprising plural lithium battery, this lithium battery can be according to the needs of the required electric energy of operational module, with in parallel or series connection or and series connection.The electric energy operation that this operational module uses supply module to provide, for example, carry out the task such as acceptance, exchange, processing, storage, transmitting of relevant information.This communication equipment can make mobile phone, notebook computer etc., and any one needs the electronic equipment of electric energy.Like this, due to the supply module of this communication equipment can be to operational module stable and continue electric energy is provided, improved high communication device security energy, and reduced the replacement frequency to battery in supply module, reduced the cost of this communication equipment operation.
Particularly, this communication equipment is smart mobile phone, and this smart mobile phone comprises operational module and supply module.Wherein, supply module adopts lithium battery mentioned above that electric energy is provided.Like this, because this lithium battery capacity is high, energy density is large, can effectively improve the stand-by time of smart mobile phone.
Illustrate above-mentioned lithium cell cathode material and preparation method thereof, cathode of lithium battery and preparation method thereof and the aspect such as lithium battery and preparation method thereof and communication equipment by multiple embodiment below.
A kind of lithium cell cathode material and preparation method thereof, lithium ion battery:
This lithium cell cathode material, as shown in Figure 1, lithium cell cathode material comprises can be with the nano material of lithium alloyage 1, be bonded in the organic group 2 on this nano material 1 surface and be adsorbed on the metallic 3 on this organic group 2 for its microstructure.Wherein, this nano material 1 is touched by organic group 2 Electricity Federations with metallic 3, and this nano material 1 is 100nm silicon grain; Organic group 2 is equal amido phenenyl acid; Metallic 3 is Ag particle.
Preparation method is as follows for this lithium cell cathode material:
Preliminary treatment: the 0.1g silica flour of about average diameter 100nm is added in the organic solvent of 20mL, after add the NH of 0.3mL amount
4under F solution (mass percent is 4%) stirring condition, react 5min, remove the oxide layer on silicon grain surface;
At nano silicon material surface bond organic group: add 0.025g equal amido phenenyl acid and 0.5mL amount organosilane ester in the solution of pre-treatment step, under stirring condition, react 6h, products therefrom is carried out to suction filtration, and clean to filtrate with absolute ethyl alcohol colourless, then by gained powder in vacuum drying chamber at 80 ℃ dry 24h;
By redox adsorbing metal particles on organic group: the powder after above-mentioned oven dry is joined again in the organic solvent of 5mL, add the salt AgNO of 0.075g amount under stirring condition
3after reaction 4h, add again the hydrazine of 0.05g, after 20h, reaction gained mixture is carried out to suction filtration, and clean to filtrate colourlessly with absolute ethyl alcohol, finally gained powder is obtained to microstructure lithium cell cathode material as shown in Figure 1 after dry 24h in vacuum drying chamber at 80 ℃.
The lithium ion battery that contains this lithium cell cathode material:
The preparation of cathode of lithium battery: after the ratio that is 6:2:2:100 according to weight ratio in lithium cell cathode material, electrodes conduct agent graphite, bonding agent CMC, aqueous solvent is mixed, in vacuum homogenizer, stir and within 4～8 hours, form uniform cathode size, this cathode size is coated on 100mm Copper Foil equably, by Copper Foil vacuum drying 24 hours, roll-in at 120 ℃, cut and make the negative plate that is of a size of 50 × 42mm.
The preparation of lithium battery anode: after the ratio that is 8:1:1:100 according to weight ratio in anode material of lithium battery, electrodes conduct agent graphite, bonding agent PVDF, solvent NMP is mixed, in vacuum homogenizer, stir and within 4～8 hours, form uniform cathode size, this anode sizing agent is coated on 100mm aluminium foil equably, by aluminium foil vacuum drying 24 hours, roll-in at 120 ℃, cut and make the positive plate that is of a size of 50 × 42mm.
After respectively positive plate, negative plate and Celgard2400 polypropylene porous film being stacked gradually according to the stacked order of positive plate/barrier film/negative plate, be wound into a rectangular cell pole piece, electrolyte is injected to battery container with the amount of 5g/Ah, sealing, makes fastening lithium ionic cell.Wherein electrolyte is EC+DEC+DMC, and wherein lithium salts is LiPF
6, its concentration is 1M.
A kind of lithium cell cathode material and preparation method thereof, lithium ion battery:
This lithium cell cathode material, the lithium cell cathode material that its microstructure is prepared with reference to embodiment 1.
Preparation method is as follows for this lithium cell cathode material:
The 0.1g silica flour of preliminary treatment: average diameter 100nm is added in the organic solvent of 5mL, after add under HF solution (mass percent the is 4%) stirring condition of 0.3mL amount and react 30min, remove the oxide layer on silicon grain surface;
At nano silicon material surface bond organic group: add 0.025g sulfanilic acid and 0.5mL amount organosilane ester in the solution of pre-treatment step, react 20h under stirring condition.Products therefrom is carried out to suction filtration, and clean to filtrate with absolute ethyl alcohol colourless, then by gained powder in vacuum drying chamber at 80 ℃ dry 8h;
By redox adsorbing metal particles on organic group: the powder after above-mentioned oven dry is joined again in the organic solvent of 20mL, add the Cu (NO of 0.075g amount under stirring condition
3)
2, reaction adds the NaBH of 0.05g after 0.5h again
4, after 6h, reaction gained mixture is carried out to suction filtration, and clean to filtrate colourlessly with absolute ethyl alcohol, finally gained powder is obtained to lithium cell cathode material after dry 8h in vacuum drying chamber at 80 ℃.
The lithium ion battery that contains this lithium cell cathode material: with reference to the preparation method of embodiment 1.
A kind of lithium cell cathode material and preparation method thereof, lithium ion battery:
This lithium cell cathode material, the lithium cell cathode material that its microstructure is prepared with reference to embodiment 1.
Preparation method is as follows for this lithium cell cathode material:
Preliminary treatment: with reference to the preprocess method to silica flour in embodiment 2;
At nano silicon material surface bond organic group: by 1g silica flour, 0.25g sulfanilic acid and 5mL amount organosilane ester add in acetonitrile (concrete title) organic solvent of 20mL amount after pretreatment, and use 6 zirconia balls to carry out ball milling 2h in 30mL high density container, products therefrom is carried out to suction filtration, and clean to filtrate with absolute ethyl alcohol colourless, then by gained powder in vacuum drying chamber at 80 ℃ dry 12h.
By redox adsorbing metal particles on organic group: with reference to the step of embodiment 2, obtain lithium cell cathode material.
The lithium ion battery that contains this lithium cell cathode material: with reference to the preparation method of embodiment 1.
Embodiment 4
Adopt CVD method on copper current collector, to prepare silicon nano thin-film, wherein film thickness suggestion <1um, then adopts organic chemical reactions and redox reaction to obtain the film after modification, and detailed process is with embodiment 1.
Comparison example
A kind of lithium cell cathode material, lithium ion battery:
Lithium cell cathode material: the silica flour that is 100nm through the pretreated average diameter of above-described embodiment 1.
Lithium ion battery: this silica flour is prepared to lithium ion battery as negative material, and concrete preparation method is with reference to the preparation method of embodiment 1.
Performance of lithium ion battery test:
The lithium ion battery of preparing in above-described embodiment 1,2,3 and comparison example is carried out to electrochemical property test.
Lithium ion battery prepared by embodiment 1 carries out charge-discharge performance test, and its result as shown in Figure 6 after tested.Can show that by Fig. 6, from finding out discharge curve first, the embedding lithium platform of this compound is more steady, there is one section of longer slope in it, then present one section of very long platform between 0.9～0.08V; Thereafter there is one section of slope in 0.35V left and right in twice discharge curve, and charging curve is less than what large variation compared with first, and just capacity slightly fluctuates.
The lithium ion battery of preparing in embodiment 1,2,3 and comparison example is carried out to cycle performance test: what this experiment set discharges and recharges system is: first test battery leaves standstill 1min, then be discharged to 0.01V with the electric current of 0.2mA by 3.0V, leave standstill again 1min, charge to 3.0V with same electric current by 0.01V, then from second step starts to be circulated to the number of times setting, finish.Its result as shown in Figure 7 after tested.The cyclical stability that can be drawn embodiment 1 and embodiment 2 by Fig. 7 is all better than comparison example, after 40 circulations of embodiment 1 respective material, capacity is still maintained at about 950mAh/g, after 40 circulations of embodiment 2 respective material, Capacitance reserve is at about 550mAh/g, after embodiment 3 respective material circulations, be just stabilized in very soon 400mAh/g, comparatively speaking, comparison example respective material cyclical stability is the poorest.Hence one can see that, and larger lifting has occurred really lithium cell cathode material cyclical stability prepared by the embodiment of the present invention.
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 (22)
1. a lithium cell cathode material, comprises
Can with the nano material of lithium alloyage; With
Be bonded in the organic group of described nano-material surface; And
Be adsorbed on the metallic on described organic group;
Wherein, described nano material and metallic electrically connect by described organic group.
2. lithium cell cathode material as claimed in claim 1, is characterized in that, the general formula of described organic group is-(CH
2) n-B-R, 0≤n≤100 in general formula, B is at least one in aliphat, aromatic series, heterocyclic group, R is at least one in benzoxy, phenylacetic acid base, benzene sulfonic acid base.
3. lithium cell cathode material as claimed in claim 1, is characterized in that, described metallic is at least one in Ag, Au, Pt, Mn, Mo, Nb, W, Ta, Fe, Cu, Ti, V, Cr, Ni, Co, Zr, Y metallic.
4. the lithium cell cathode material as described in as arbitrary in claim 1～3, is characterized in that, described nano material is at least one in the nano simple substance particle, nano wire, nanotube, nanofiber, nano thin-film, Nanoalloy particle of M element; Wherein, described M element is at least one in Si, Sn, Ge, Pb, Sb, Al, Zn.
5. the lithium cell cathode material as described in as arbitrary in claim 4, is characterized in that, described nano simple substance particle is or/and the particle diameter of Nanoalloy particle is 50～200nm.
6. the lithium cell cathode material as described in as arbitrary in claim 1～3, is characterized in that, described metallic accounts for 2～10% of described lithium cell cathode material gross mass.
7. the lithium cell cathode material as described in as arbitrary in claim 1～3, is characterized in that, described organic group accounts for 2～8% of described lithium cell cathode material gross mass.
8. the preparation method of the lithium cell cathode material as described in as arbitrary in claim 1～7, comprises the steps:
By described can be with the nano material of lithium alloyage, contain the bonding organic substance at described nano-material surface organic group, the first organic solvent mixes, stirring reaction or ball milling carry out Separation of Solid and Liquid, collecting precipitation after 6～20 hours;
After described precipitation is dry, add in polar solvent, add slaine, stir and add reducing agent after 0.5～4 hour, make the metal ion generation redox reaction in itself and described slaine, after 6～20 hours, carry out Separation of Solid and Liquid, purifying, obtains described lithium cell cathode material.
9. the preparation method of lithium cell cathode material as claimed in claim 8, be characterised in that: by described can with the nano material of lithium alloyage with contain before the bonding organic substance at described nano-material surface organic group, the first organic solvent mix, also comprise described nano material carried out to pretreated step:
By described nano material and HF or NH
4f solution mix and blend reacts, and removes the oxide layer of described nano-material surface.
10. the preparation method of lithium cell cathode material as claimed in claim 8, is characterised in that: the mass ratio of described nano material and organic substance consumption is 4:1～10:1.
The preparation method of 11. lithium cell cathode materials as claimed in claim 8, be characterised in that: described organic substance is 3, at least one in the primary amine of 4,5-trifluoromethyl aniline, p-aminobenzoic acid, equal amido phenenyl acid, sulfanilic acid and aliphat, aromatic series and heterocycle or its mixture.
The preparation method of 12. lithium cell cathode materials as claimed in claim 8, is characterised in that: described the first organic solvent is at least one in acetonitrile, methyl alcohol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, formic acid, acetic acid, pentane, hexane, octane.
The preparation method of 13. lithium cell cathode materials as claimed in claim 8, is characterised in that: the mass ratio of described precipitation, slaine and reducing agent consumption is 4:1:1～10:1:1.
The preparation method of 14. lithium cell cathode materials as claimed in claim 8, is characterised in that: described slaine is at least one soluble-salt in Ag salt, Au salt, Pt salt, Mn salt, Mo salt, Nb salt, W salt, Ta salt, Fe salt, Cu salt, Ti salt, V salt, Cr salt, Ni salt, Co salt, Zr salt, Y salt.
The preparation method of 15. lithium cell cathode materials as claimed in claim 8, is characterised in that: described reducing agent is at least one in hydrazine, sodium borohydride, sodium thiosulfate, iron ammonium sulfate, vulcanized sodium.
16. 1 kinds of cathode of lithium battery, comprise collector and are combined in the negative material that contains on described collector, it is characterized in that: described negative material is the arbitrary described lithium cell cathode material of claim 1～7.
17. 1 kinds of cathode of lithium battery preparation methods, comprise the steps:
By arbitrary claim 1～7 described lithium cell cathode material and electrodes conduct agent, bonding agent and solvent, and be mixed with cathode size;
Described cathode size is coated on collector;
The described collector that is coated with cathode size is dried to processing, roll-in, cutting, obtains cathode of lithium battery.
18. cathode of lithium battery preparation methods as claimed in claim 17, are characterised in that: the weight ratio of described lithium cell cathode material, electrodes conduct agent, bonding agent and solvent is 6:(1.5 ~ 3.5): (1.5 ~ 3.5): (90 ~ 100).
19. 1 kinds of lithium batteries, is characterized in that, described lithium battery comprises the cathode of lithium battery described in claim 16.
20. lithium batteries as claimed in claim 19, are characterised in that: described lithium battery is that lithium ion battery is or/and lithium polymer battery.
21. 1 kinds of lithium battery preparation methods, comprise the steps:
Prepare lithium battery anode and negative pole, described cathode of lithium battery is prepared from by the cathode of lithium battery preparation method described in claim 17 or 18;
Described lithium battery anode, barrier film, described cathode of lithium battery are stacked gradually, and reel, make battery battery core;
Described battery core is packed in battery container, the electrolyte that reinjects, sealing, makes lithium battery.
22. 1 kinds of communication equipments, comprise operational module and supply module, and described supply module comprises the lithium battery described in claim 19; 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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Application publication date: 20140514 |