CN206451769U - A kind of secondary cell - Google Patents
A kind of secondary cell Download PDFInfo
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- CN206451769U CN206451769U CN201621451679.7U CN201621451679U CN206451769U CN 206451769 U CN206451769 U CN 206451769U CN 201621451679 U CN201621451679 U CN 201621451679U CN 206451769 U CN206451769 U CN 206451769U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The utility model discloses a kind of secondary cell, including：First electrode and the second electrode immediately below first electrode, first electrode is parallel to each other with second electrode, provided with hole-conductive layer and ion conducting layer between first electrode and second electrode, the upper and lower surface of hole-conductive layer and ion conducting layer is contacted with first electrode and second electrode respectively.Secondary cell of the present utility model can realize high power and high power capacity.
Description
Technical field
The utility model is related to cell art, more particularly to a kind of secondary cell.
Background technology
In the range of world in recent years, battery is communicated in electronics, is widely used in the portable electric appts such as computer,
Also, used in the fixation such as the moving bodys such as following electric car and electric power smoothing system, the practical of large-sized battery system enjoys the phase
Treat, progressively as nucleus equipment.The chemical energy of chemical substance in battery is converted into by battery by electrochemical redox reaction
Electric energy, secondary cell refers to by way of charging can to make after battery discharge the battery that active material is activated and is continuing with.
Lithium rechargeable battery is now widely available, and in general lithium rechargeable battery, positive electrode active materials are
Transition metal oxide, negative active core-shell material is the material that can absorb/release lithium ion (for example, lithium metal, lithium alloy, gold
Belong to oxide and carbon material), additionally comprise nonaqueous electrolytic solution, barrier film.But, original lithium rechargeable battery, unit
The power and capacity of weight or unit volume have progressivelyed reach the limit, it is impossible to meet market needs.
Utility model content
In order to solve the above technical problems, the secondary electricity of high power and high power capacity can be realized the utility model proposes a kind of
Pond.
The technical solution adopted in the utility model is to design a kind of secondary cell, including：First electrode and located at first electricity
Second electrode immediately below pole, first electrode is parallel to each other with second electrode, and hole is provided between first electrode and second electrode
The upper and lower surface of conducting shell and ion conducting layer, hole-conductive layer and ion conducting layer connects with first electrode and second electrode respectively
Touch.The top surface of first electrode is provided with the first colelctor electrode, and the top surface of the second electrode is provided with the second colelctor electrode.
In one embodiment, uniform intervals are placed with through hole, through hole and are filled with ion-conductive material in hole-conductive layer
Form ion conducting layer.
It is preferred that, it is provided with first electrode in P-type semiconductor, second electrode and is provided with N-type semiconductor.
It is preferred that, the top surface of hole-conductive layer and bottom surface are equipped with electrolyte layers, and electrolyte layers are by electrolyte or solid electrolyte
It is covered on the surface of hole-conductive layer and is formed.
It is preferred that, hole-conductive layer is made up of titanium oxide, silicon or ceramic material.
It is preferred that, the thickness range of hole-conductive layer is 6 μm~25 μm.
It is preferred that, the first colelctor electrode and the second colelctor electrode are made of stainless steel.
It is preferred that, the outer surface of first electrode and second electrode is coated with aluminum plastic film.
Compared with prior art, the utility model is provided with hole-conductive layer and ion between the first electrode and the second electrode
The ion produced at conducting shell, first electrode or second electrode is moved by ion conducting layer between first electrode and first electrode
Dynamic, ion is moved between first electrode and second electrode, so secondary cell can realize high power capacity.First electrode or the second electricity
The hole of pole is moved by hole-conductive layer between first electrode and second electrode, and hole is smaller than ion, and higher shifting
Dynamic degree, so secondary cell can realize high output.
Brief description of the drawings
The utility model is described in detail with reference to embodiment and accompanying drawing, wherein：
Fig. 1 is the structure chart of preferred embodiment in the utility model；
Fig. 2 is the gravimetric energy density figure of secondary cell and lithium battery in the utility model；
Fig. 3 is the IC discharge capacity figures of first embodiment, sixth embodiment and comparing embodiment in the utility model.
Embodiment
As shown in figure 1, the utility model proposes secondary cell, including：First electrode 10, second electrode 20, ion are passed
Conducting shell 30 and hole-conductive layer 40.First electrode 10 is parallel to each other with second electrode 20 and position is relative, by ion conducting layer 30
Separated with hole-conductive layer 40, by least one of both, first electrode 10 and second electrode 20 can not be physically contacted.
First electrode 10 has positive pole function, and second electrode 20 has negative pole function.When implementing electric discharge, first electrode 10
Current potential is higher than second electrode 20, and electric current flows to second electrode 20 from first electrode 10 by external load.It is outside when implementing charging
The high potential terminal of power supply is connected with first electrode 10, and the low potential terminal of external power source is connected with second electrode 20.Herein,
One electrode 10 is made up of the first collector 110 and the positive pole being in contact with it, second electrode 20 be by the second collector 120 and with
Its negative pole contacted composition.
As shown in figure 1, ion conducting layer 30 is contacted with first electrode 10 and second electrode 20, ion conducting layer 30 is in sky
At the linear elongated hole of cave conducting shell 40.Ion conducting layer 30 can be the liquid such as electrolyte or pastel.Electric discharge
When, the cation produced at second electrode 20 is moved to first electrode 10 by ion conducting layer 30, when charging, the
Ion is produced at one electrode 10, second electrode 20 is moved to by ion conducting layer 30, ion is from first electrode 10 to the second electricity
Pole 20 is moved, so the current potential of first electrode 10 becomes higher than second electrode 20.
Ion can be alkali metal or alkaline-earth metal ions for example, and first electrode 10 contains alkali metal or alkaline earth gold
Belong to class compound.Second electrode 20 can then be embedded in move out alkali metal or alkaline-earth metal class ion.Secondary cell 100 discharge when
Wait, alkali metal or alkaline-earth metal ions are moved out from second electrode 20, by ion conducting layer 30, moved to first electrode 10.
When secondary cell 100 charges, alkali metal or alkaline-earth metal ions are moved out by ion conducting layer 30 from first electrode 10
Move, absorbed by second electrode 20 to second electrode 20.In addition, the ion conducted by ion conducting layer 30, can also be simultaneously
Contain alkali and alkaline earth metal ions ion.
In preferred embodiment, first electrode 10 contains p-type semiconductor, and the hole concentration of P-type semiconductor is much larger than freely
Electron concentration, in charge or discharge, hole is moved by first electrode 10.Hole-conductive layer 40 and first electrode 10 and second
Electrode 20 is contacted.When electric discharge, the hole of first electrode 10 is moved by external load to second electrode 20, first electrode 10
Hole is received by hole-conductive layer 40.Wait when charging, the hole of first electrode 10 is electric to second by hole-conductive layer 40
Pole 20 is moved, and first electrode 10 receives hole from external power source.
When discharge and recharge, ion is not only in movement, hole is also in movement.Specifically, when electric discharge, it is more than
The ion produced at second electrode 20 is moved by ion conducting layer 30 to first electrode 10, and hole is in first electrode 10, outside
Circulated successively in load, second electrode 20 and hole-conductive layer 40, and generate the electricity of first electrode 10 and second electrode 20
Potential difference.In addition, when charging, being not only the ion produced at first electrode 10 by ion conducting layer 30 to second electrode 20
Mobile, hole is also circulated between first electrode 10, hole-conductive layer 40, second electrode 20 and external power source successively.
The ion produced at first electrode 10 or second electrode 20 is by ion conducting layer 30 in first electrode 10 and the
Moved between two electrodes 20, ion is moved between first electrode 10 and second electrode 20, so secondary cell 100 can realize Gao Rong
Amount.Hole is moved by hole-conductive layer 40 between first electrode 10 and second electrode 20, and hole is smaller than ion, and higher
Degree of excursion, so secondary cell 100 can realize high output.Fig. 2 is the secondary cell 100 of preferred embodiment and general
The gravimetric energy density figure comparison diagram of secondary cell, it will be evident that secondary cell of the present utility model 100 is exerted oneself from Fig. 2
Characteristic, which has, obviously to be improved.
The existing chemical cell that ion reception and registration is carried out by ion conducting layer 30 of secondary cell 100 of the present utility model, again
There is the semi-conductor cell for carrying out hole-conductive by hole-conductive layer 40 from p-type semiconductor first electrode 10, both are contained simultaneously
Characteristic.Secondary cell 100 can be described as the hybrid battery of chemical cell and physical battery (semi-conductor cell).In this practicality
In new secondary cell 100, ion conducting layer 30 can reduce the usage amount of electrolyte, even if the electricity of first electrode 10 and second
Pole 20 comes in contact generation internal short-circuit, and the temperature that can also suppress secondary cell 100 rises.Also, of the present utility model two
The capacity decline in sudden discharge of primary cell 100 is also smaller, and cycle performance is also more excellent.Along with the conduct of first electrode 10
P-type semiconductor, second electrode 20 can be carried further as n-type semiconductor, the capacity of secondary cell 100 and performance of exerting oneself
Rise.
Whether first electrode 10 and second electrode 20 are respectively p-type and n-type semiconductor, can be by determining Hall effect
(Hall effect) judges.Hall effect understands that print adds magnetic field on electric current, then in the electric current side vertical with magnetic direction
Voltage is produced upwards.Pass through the direction of voltage, it is possible to determine that p-type or n-type semiconductor.
As shown in figure 1, in preferred embodiment, ion conducting layer 30 is in the position in the hole of hole-conductive layer 40, but
It is that the utility model is not limited to this.Ion conducting layer 30 is located at the position away from hole-conductive layer 40 also possible.
In addition, as described above, when charging and discharging, ion and hole pass through ion conducting layer 30 and hole-conductive layer 40 respectively
Conducted.In fact, when charge or discharge, only by ion conducting layer 30 or hole-conductive layer 40, only conduct from
Son or hole are also possible.For example when discharging, even if without ion conducting layer (such as electrolyte) 30, only hole is passed
Lead also possible.Or during charging, without hole-conductive layer 40, only ion by ion conducting layer 30 in first electrode 10
Conduct also possible between second electrode 20.In addition, hole-conductive layer 40 can also form one with ion conducting layer 30,
That is, it is also possible that same portion's material can conduct both ion and hole.
Described in detail below for first electrode 10：
Composite oxides of the first electrode 10 containing alkali metal or alkaline-earth metal.For example, in alkali metal at least lithium and sodium
One kind, alkaline-earth metal then has magnesium.Composite oxides are the positive active materials of secondary cell 100.Such as, first electrode 10 by
The anode electrode material that composite oxides and positive electrode binder are mixed is formed.In addition, further being mixed in anode electrode material
Conductive agent can also.In addition, composite oxides are not limited to one kind, can also containing plural species.
Composite oxides contain p-type semiconductor composite oxides.For example, the p-type that can play p-type semiconductor function is answered
Close oxide and contain lithium and nickel, and be doped with least one of antimony, lead, phosphorus, boron, aluminium plus gallium.This based composite oxide can
With with LixNiyMzOαRepresent.Wherein, 0<x<3rd, y+z=1,1<α<4.In addition, M is as p-type semiconductor function element, by antimony,
At least select a kind of in lead, phosphorus, boron, the group of aluminium plus gallium composition, by doping, p-type composite oxides produce fault of construction, thus
Form hole.For example, p-type composite oxides contain metal-doped lithium nickelate, it is more satisfactory.For example, p-type is compound
Oxide can be the lithium nickelate of Sb doped.
In addition, composite oxides are also more satisfactory by multiple types mixing, for example, composite oxides are contained by p-type
Composite oxides and the solid solution shape composite oxides of solid solution formation.Solid solution is by p-type composite oxides and solid solution shape
Composite oxides are formed.Solid solution shape composite oxides easily form the solid solution of stratiform with nickel acid, and the structure of solid solution is easy
In hole movement, such as a kind of LiMn2O4 (Li of solid solution shape composite oxides2MnO3), wherein the valence mumber of lithium is 2.
In addition, composite oxides and then olivine-type composite oxides containing olivine structural are also more satisfactory.
By olivine structural, when p-type composite oxides formation hole, it can effectively suppress the deformation of first electrode 10.
Also, olivine-type composite oxides contain lithium and manganese, the valence mumber of lithium is also more satisfactory greatly than 1, and now, lithium ion is easy to
Mobile, hole is also easy to be formed.For example, olivine-type composite oxides are LiMnPO4.In addition, composite oxides can be with
Contain p-type composite oxides, the composite oxides of the good olivine structural of solid solution shape composite oxides.Pass through such multiple types
Composite oxides are mixed, and the cycle performance of secondary cell 100 can be lifted.
For example, composite oxides can contain LixNiyMzOα、Li2MnO3And LiβMnPO4, wherein, 0<x<3rd, y+z=1,1<
α<4、β>1.Other composite oxides can also contain LixNiyMzO α, Li2MnO3And LiγMnSiO4, wherein, 0<x<3rd, y+z=
1、1<α<4、γ>1.Or, composite oxides can also contain Li1+x(Fe0.2Ni0.2)Mn0.6O3、Li2MnO3And LiβMnPO4,
Wherein, 0<x<3、β>1.
Such as, the active material of first electrode 10, can be lithium nickelate, lithium manganese phosphate, LiMn2O4, nickel ion doped and it
Solid solution, or, various denaturation bodies (antimony, aluminium, the cocrystallization thing of the metal such as magnesium) etc. composite oxides and various materials
The product synthesized by chemistry or physical method.Other for example, composite oxides by Sb doped nickel acid, lithium manganese phosphate and lithium
The product that Mn oxide is synthesized by mechanical collision physics, or the product synthesized by 3 composite oxides chemical coprecipitations is also
Can with.In addition, the composite oxides can contain fluorine.For example, composite oxides can also use LiMnPO4F.Therefore, i.e.,
The electrolyte containing lithium hexafluoro phosphate is produced hydrofluoric acid, the change of the characteristic of composite oxides can be suppressed.
The anode electrode material that first electrode 10 is mixed by composite oxides, positive electrode binder and conductive agent is formed.
For example, positive electrode binder can include the acrylic resin formed in acrylic resin, first electrode 10.For example, positive pole
Adhesive includes the rubber-like polymer containing polyacrylic acid unit.As rubber-like polymer, HMW and low molecule amount
Mixed with polymers into being more satisfactory.When therefore, by the mixed with polymers with different molecular weight, more resistant to hydrogen fluorine
Acid, the interference of hole transport is also suppressed.
For example, positive electrode binder is by the fine rubber grain adhesive of modified propylene (BM-520 of Japanese Zeon Co., Ltds),
Carboxymethyl cellulose (Carboxymethylcellulose with thickening power：) and the soluble fine rubber of modified propylene CMC
(BM-720 of Japanese Zeon Co., Ltds) mixing is made.Preferably use by containing acrylic acid series group, (Japanese Zeon is limited
Company SX9172) as positive electrode binder polyacrylic acid monomers adhesive.In addition, conductive agent can use acetylene black, section
Qin is black, and various graphite are used alone or in combination.
When that is mentioned in following article carries out the secondary cell of nail puncture test and impact test, under test conditions, heating
Therefore the time of temperature short circuit internally can locally exceed hundreds of degrees Celsius of, and positive electrode adhesive is by being easy to melt or burning
The material composition of mistake is in accordance with preferable.For example, as adhesive, at least using a kind of crystalline melt point and decomposition temperature 250
Material more than DEG C.
For example, the rubber-like polymer containing caoutchouc elasticity, and be the bonding of non-crystalline type high temperature resistant (320 DEG C)
Agent is in accordance with preferable.For example, rubber-like polymer has the acrylic groups of the unit containing polyacrylonitrile.In such case
Under, acrylic resin, which has, contains polyacrylic acid as the rubber-like polymer of elementary cell.Using such adhesive,
Electrode caused by resin is deformed when softening or burning and lose can be suppressed to peel off from collector, result burst excess current is played
When, the abnormal overheat of battery can also be suppressed.In addition, the itrile group adhesive by representative of polyacrylonitrile, is less susceptible to hinder empty
The movement in cave, is also applicable in the secondary cell 100 of this embodiment.
By above-mentioned material as positive electrode adhesive, during secondary cell for assembling 100, crackle is difficult to produce in first electrode 10
Raw, it can keep high yield rate.In addition, by using with material of the acrylic as positive electrode binder, it is internal electric
Resistance reduction, can suppress the hindering factor of the performance of p-type semiconductor first electrode 10 performance.
In addition, in acrylic positive electrode binder, there is ionic conductivity glass or P elements is also in accordance with preferable.By
This, positive electrode binder will not become resistance, it is difficult to enclose sunken electronics, can suppress the heating of first electrode 10.Specifically, propylene
Contain P elements or ionic conductivity glass in base positive electrode binder, dissociation reaction and the diffusion of lithium can be promoted.Pass through
Containing these materials, allyl resin layer can coat active material, can react what is produced with inhibitory activity material and electrolyte
Gas.
Further, P elements or ionic conductivity glass are contained in allyl resin layer, current potential slows down, and reduces activity
The oxidizing potential of material, while will not interfere with the movement of lithium ion.In addition, the proof voltage excellent performance of allyl resin layer.Cause
This, in first electrode 10 during high voltage, can realize the ion conduction structure of high power capacity and high output can form.In addition, expanding
Dissipate speed to accelerate, resistance step-down, temperature when can suppress high output rises, and therefore, life-span and security can also be lifted.
Described in detail below for second electrode 20：
Second electrode 20 can absorb and discharge the ion produced in first electrode 10 while can receive hole.As
The active material of second electrode 20, at least containing graphene and silicon.Furthermore, various native graphites, Delanium, graphene, silicon
Composite material (silicide), the oxide of the material based on silicon, the alloy material of titanium, and closed alone or in combination containing various
The material of gold composition is made.For example, second electrode 20 includes graphene.In this case, second electrode 20 is that n-type is partly led
Body.Wherein, the graphene number of plies is less than 10 layers.Graphene can contain CNT (Carbon nanotube：CNT).Especially
, while the silicon included in second electrode 20 can improve the storage efficiency of ion (cation) of second electrode 20, connect
Efficiency by hole is also very high.Further, since graphene and silica are not heaters, so as to improve secondary cell 100
Security.
As described above, it is in accordance with preferable that second electrode 20, which is n-type semiconductor,.Second electrode 20 have containing graphene and
The material of silicon.Material a, for example, SiOxa(xa<2).In addition, second electrode 20, by using graphene and/or silicon,
Even if when the internal short-circuit generation of secondary cell 100, and hardly generating heat, the rupture of secondary cell 100 can be suppressed.This
Outside, can also adulterate alms giver in second electrode 20.For example, metallic element is used as donor doping in second electrode 20.Metallic element,
For example, alkali metal or transition metal.As alkali metal, for example, copper, lithium or sodium and potassium can be doped.Or, transition metal, titanium
Or zinc can be doped.
Second electrode 20 can have the graphene of lithium doping.For example, organolithium is contained by heating, second electrode 20
Material can carry out lithium doping.Or, it is doped by the way that lithium metal is attached in second electrode 20.Preferably, second electrode 20 contains
There are the graphene and silicon of lithium doping.Second electrode 20 contains halide.Containing halide, even if lithium hexafluoro phosphate is used as electrolyte
Using hydrofluoric acid is produced, the performance change of second electrode 20 can be suppressed.For example, containing the plain halide of fluorine.Second electrode 20 contains
There is SiOxaF.Or contain iodine halide.Second electrode 20 from by mixing the adhesive of negative electrode active material and negative electrode and
Obtained negative material is formed.Can be identical with positive electrode binder as negative electrode adhesive.In addition, the negative material can enter one
Walk hybrid conductive material.
Described in detail below for ion conducting layer 30：
Ion conducting layer 30 can be liquid, gelinite and solid.As ion transport part material 30, liquid (electrolyte) is just
It is good to be used.Electrolyte is that salt dissolves in a solvent.Salt can select more than one or two kinds of to mix from the group of consisting of
Conjunction is used：LiPF6、LiBF4、LiClO4、LiSbF6、LiAsF6、LiCF3SO3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiC
(SO2CF3)3、LiN(SO3CF3)2、LiC4F9SO3、LiAlO4、LiAlCl4, LiCl, LiI, double (pentafluoroethane sulphonyl) imines of lithium
(LiN(SO2C2Fb)2:Lithium Bis(pentafluoro-ethane-sulfonyl)Imide:LiBETI), double (trifluoros of lithium
Sulfonyl methane) imines (Lithium Bis (Trifluoromethanesulfonyl) Imide:LiTFS) the group of composition.
In addition, as solvent, can be from ethylene carbonate (Ethylene Carbonate:), EC ethylene fluoride ester
(Fluorinated Ethylene Carbonate:FEC), dimethyl carbonate (Dimethyl Carbonate:), DMC carbonic acid
Diethylester (Diethyl Carbonate:DEC), methyl ethyl carbonate (Methyl Ethyl Carbonate:MEC) the group of composition
The one or more kinds of mixture of middle selection.
In addition, in order to ensure that vinylene carbonate (Vinylene can also be added in security during overcharge, electrolyte
Carbonate:), VC hexamethylene (Cyclohexylbenzene:CHB), propane sultone (Propane Sultone:), PS propylene
Sulphite (Propylene Sulfite:PRS), glycol sulfite (Ethylene Sulfite:), ES azophenlyene sulfuric acid first
Ester (phenazine methosulfate:PMS).
Described in detail below for hole-conductive layer 40：
Hole-conductive layer 40 is solid or gelinite.Hole-conductive layer 40 at least with first electrode 10 and second electrode 20
One then.When using electrolyte as ion conducting layer 30, hole-conductive layer 40 is preferably provided with porous layer.This
In the case of, electrolyte connects first electrode 10 with second electrode 20. for example, hole-conductive layer 40 has pottery by the hole of porous layer
Ceramic material.As an example, hole-conductive layer 40 includes the porous membrane layer containing inorganic oxide filler.For example, inorganic
Oxide filler is preferably by aluminum oxide (α-Al2O3) it is principal component, hole is in oxidation aluminium surface movement.In addition, Porous film layer can
Further to contain ZrO2-P2O5.Or, as hole-conductive layer 40, titanium oxide or silicon can also be used.
Hole-conductive layer 40 is not shunk preferably by temperature change.The preferably low resistance of hole-conductive layer 40.For example,
As hole-conductive layer 40, then using the non-woven fabrics of the ceramic material carried.Non-woven fabrics is hardly shunk by temperature change.
In addition, non-woven cloth, with proof voltage and antioxygenic property, shows low resistance.Therefore, supatex fabric is relatively suitable as
The material of hole-conductive layer 40.
Hole-conductive layer 40 is preferably provided with the function of barrier film.Hole-conductive layer 40 has in the range of the use of secondary cell 100
Tolerance composition, when being not limited to secondary cell 100 and lose semiconductor machine energy.It is used as hole-conductive layer 40, it is preferred to use
Contain aluminum oxide (α-Al2O3) non-woven fabrics.The thickness of hole-conductive layer 40 is not limited, it is considered to during design capacity, is preferably designed
Thickness is 6 μm~25 μm.In addition, preferably mixing ZrO2-P2O5 in aluminum oxide.So, the conduction in hole can be easier to.
Described in detail below for the first collector 110, the second collector 120：
For example, the first collector 110 and the second collector 120 are made of stainless steel.It therefore, it can the expansion electricity of low cost
Position potential range.
The following is the description of embodiment of the present utility model.However, the utility model is not limited to following examples.
Comparing embodiment：
By the BC-618 of the lithium-nickel-manganese-cobalt of Sumitomo 3M Co., Ltds, the PVDF#1320 (weights of solid constituent 12 of Kuraha companies
Measure 1-METHYLPYRROLIDONE (NMP) solution of part), and acetylene black is by weight 3：1：0.09, and further N- methyl pyrroles
Pyrrolidone (NMP), is stirred in a both arms mixer, to prepare positive electrode material.On the aluminium foil of 13.3 μm of thickness
Positive electrode material is coated with, after drying, roll-in is carried out, obtains 155um gross thickness, then, cut into slices by specific dimensions,
Anode electrode is made.
By artificial blacklead, the BM-400B of the SB rubber particles adhesive of Nippon Zeon
(parts by weight of solid constituent 40), and carboxymethyl cellulose (Carboxymethylcellulos：CMC 100) are pressed:2.5:1 weight
Than adding suitable quantity of water and being stirred in double-arm mixer, make negative electrode material.It is negative for coating on 10um copper foil in thickness
Pole electrode material, carries out roll-in after drying, obtains thickness about 180um, then, cut into slices by specific dimensions, negative pole is made
Electrode.
Thickness is put between both positive and negative polarity for 20um polypropylene micro-porous film as barrier film, makes stepped construction, cutting is
The size of setting, is inserted into electric groove tank.By ethylene carbonate (ethylene carbonate：EC), dimethyl carbonate (dimethyl carbonate：
) and methyl ethyl carbonate (methyl ethyl carbonate DMC：MEC electrolyte is made in the LiPF6 that 1M is dissolved in the solvent) mixed.Dry
Electrolyte is injected in dry air ambient and is stood after a period of time, it is electric 20 minutes with the pre-charge equivalent to 0.1C, then
Sealing, has been made laminated type lithium rechargeable battery.And certain time aging afterwards, is placed under normal temperature environment.
First embodiment：
The lithium nickelate (manufacture of mine company of Sumitomo Metal Industries) that the weight of antimony (Sb) 0.7% is adulterated, Li1.2MnPO4(Dow
The Lithiated Metal Phosphate II of Chemical Company manufactures), and Li2MnO3(Zhenhua E-Chem
Co., the ZHFL-01 of ltd manufactures) mixed according to 54.7%, 18.2%, 18.2% part by weight, manufactured in Xi Chuan companies
In AMS-LAB (mechanical fusion), handled 3 minutes with 1500rpm rotational speed, the active material of first electrode 10 has been made.
Then, by active material, acetylene black is as conductive processing, and (Japanese Zeon is limited for the monomeric cement of polyacrylic acid composition
Company SX9172) it is 92 by weight：3：5, methyl pyrrolidone (NMP) is added, is stirred in both arms mixer, to make
Standby positive electrode material.
Positive electrode material is coated with the SUS paper tinsels (manufacture of Zhu Jin Materials Co., Ltd of Nippon Steel) of 13 μm of thickness, after drying
Roll-in is carried out, obtained surface density is 26.7mg/cm2, then, cut into slices by specific dimensions, first electrode 10 be made.Pass through
The Hall effect of first electrode 10 is determined, can confirm that first electrode 10 is p-type semiconductor.
By grapheme material (" the xGnP Graphene Nanoplatelets H of XG Sciences, Inc. manufactures
Type "), silicon oxide sioxa(" the SiO of Shanghai Shanshan Science and Technology Co., Ltd's manufacturex") according to 56.4%, 37.6% weight ratio
Example mixing, in the NOB-130 (nobilta) that Xi Chuan companies manufacture, is handled 3 minutes with 800rpm rotational speed, is made
The active material of negative pole.Then, by active material, monomeric cement (the Japanese Zeon Co., Ltds of polyacrylic acid composition
SX9172 it is) 95 by weight：5, methyl pyrrolidone (NMP) is added, is stirred in both arms mixer, to prepare negative pole
Electrode material.
Negative electrode material is coated with the SUS paper tinsels (manufacture of Zhu Jin Materials Co., Ltd of Nippon Steel) of 13 μm of thickness, after drying
Roll-in is carried out, obtained surface density is 5.2mg/cm2, then, cut into slices by specific dimensions, second electrode 20 be made.
Non-woven fabrics that thickness is 20um containing alpha-aluminium oxide (paper company of Mitsubishi manufacture " Nano X ") is put in as barrier film
Between first electrode 10 and second electrode 20, lamination is made, cutting is the size of setting, is inserted into battery case.It is right
Non-woven fabrics containing Alpha-alumina carries out impregnation process, using processing material be Novolyte technologies companies "
Novolyte EEL-003 " (vinylene carbonate (vinylene carbonates：) and double (oxalic acid) boric acid of lithium (double (oxalic acid) boron of lithium VC
Hydrochlorate：LiBOB 2 weight % and 1 weight) are added respectively).
Then, by EC (ethylene carbonate), DMC (dimethyl carbonate) and PC (propene carbonate) by volume 1:1:1 mixes
1M LiPF is dissolved in the solvent closed6Electrolyte is made.One section of electrolyte and standing are injected in dry air ambient
It is electric 20 minutes with the pre-charge equivalent to 0.1C after time, then seal, laminated type lithium rechargeable battery has been made.And
And afterwards, certain time aging is placed under normal temperature environment.
Second embodiment：
In a second embodiment, Li is used1.2MnPO4F replaces the Li in first embodiment1.2MnPO4, to prepare secondary cell.
3rd embodiment：
In the third embodiment, Li is used1.4MnPO4F replaces the Li in first embodiment1.2MnPO4, to prepare secondary cell.
Fourth embodiment：
In the fourth embodiment, by the Li in first embodiment1.2MnPO4It is changed to Li1.3(Fe0.2Ni0.2)Mn0.6O3, with
Prepare secondary cell.
5th embodiment：
In the 5th embodiment, by the graphene in first embodiment by volume 3:1 addition Cnano
The CNT of Technology Limited manufactures, to prepare secondary cell.
Sixth embodiment：
In the sixth embodiment, at the second electrode 20 of first embodiment, the lithium metal foil of 1/7 area is attached, to prepare
Secondary cell.
7th embodiment：
In the 7th embodiment, when the negative electrode material of first embodiment makes, in below 10ppm moisture environment,
Weight is added than the lithium powder for 0.06%, to prepare secondary cell.
8th embodiment：
In the 8th embodiment, when the negative electrode material of first embodiment makes, addition weight is than for 0.09%
FeF3Powder, to prepare secondary cell.
9th embodiment：
In the 9th embodiment, when the negative electrode material of first embodiment makes, addition weight is than the iodine for 0.03%
Element, to prepare secondary cell.
Tenth embodiment：
In the tenth embodiment, when the negative electrode material of first embodiment makes, addition weight is than the sodium for 0.06%
Powder, to prepare secondary cell.
11st embodiment：
In the 11st embodiment, when the negative electrode material of first embodiment makes, addition weight is than for 0.06%
Potassium powder, to prepare secondary cell.
12nd embodiment：
In the 12nd embodiment, when the negative electrode material of first embodiment makes, addition weight is than for 0.06%
Titanium valve, to prepare secondary cell.
13rd embodiment：
In the 13rd embodiment, when the negative electrode material of first embodiment makes, addition weight is than for 0.06%
Zinc powder, to prepare secondary cell.
14th embodiment：
In the 14th embodiment, 250ppm adds ZrO by volume in the non-woven fabrics of first embodiment2-P2O5, to make
Standby secondary cell.
15th embodiment：
In the 15th embodiment, when the negative electrode material of first embodiment makes, addition weight than for 0.8% it is pungent
Sour lithium, to prepare secondary cell.
As described above, the battery being made from first embodiment to the 15th embodiment and comparing embodiment, passes through
Following methods are evaluated.
Battery initial capacity is evaluated：
The battery of comparing embodiment in 2V-4.3V potential ranges 1C discharge capacities as 100, other each secondary cells
Capacity is compared with it.In addition, being shaped as this primary cell is square, laminated type.Other capacity evaluation can also 2V-4.6V electricity
Carried out in the range of position.Further, 10C/1C discharge capacity ratio is also determined.
Puncture test：
The secondary cell of fully charged state, by diameter 2.7mm irony wire nail with the speed of 5mm/ seconds in the case of normal temperature
Puncture, febrile state and battery outward appearance when observation is penetrated.As a result reference table 1.In table 1, the temperature of secondary cell and outer
See the secondary cell not changed to be expressed as " OK ", the temperature and outward appearance of secondary cell have the secondary cell table changed
It is shown as " NG ".
Overcharge test：
Maintain the electric current of charge rate 200% more than 15 minutes, whether changed and judged by battery outward appearance.As a result refer to
Table 1.In table 1, do not occur abnormal secondary cell and be expressed as " OK ", change the secondary cell table of (bulging or rupture)
It is shown as " NG ".
Normal temperature life performance：
First embodiment to the 15th embodiment and comparing embodiment secondary cell, in voltage range 2V-4.3V,
After 25 DEG C of 1C/4.3V chargings, 1C/2V electric discharges circulate 3000 times, compared with the capacity of first time, compare the sustainment rate of capacity.
Evaluation result：
Following table shows above-mentioned evaluation result.
The secondary cell of comparing embodiment, is so-called general lithium rechargeable battery.In the secondary of comparing embodiment
It is unrelated with puncturing speed in battery, there is significant heating after 1 second.In contrast to this, the secondary cell of first embodiment, significantly
Inhibit puncture after overheat.Decompose and check the battery after puncture test, the secondary cell septation of comparing embodiment is big
Scope is melted, in the first embodiment, and the nonwoven cloth diaphragm containing ceramics also maintains original shape.It is therefore seen that, the nothing containing ceramics
Cloth is spun, when puncture causes short circuit then to be generated heat, structure is not also destroyed, it is suppressed that the expansion of short position,
Prevent notable overheat.Positive electrode binder is discussed herein.In the secondary cell of comparing embodiment, positive pole is used as by using PVDF
Adhesive, when puncturing speed attenuating, it is impossible to suppress the generation of overheat.Decompose and check the secondary cell of comparing embodiment, aluminium foil
The active material of (collector) is peeled off.Its reason considers as follows.
When in the secondary cell that nail is pierced into comparing embodiment, occurring internal short-circuit, and then generation Joule heat, PVDF (is tied
Brilliant 174 DEG C of fusing point) dissolving cause positive pole to deform.When active material comes off, resistance is reduced, and more easily electric current passes through,
The generation of overheat is promoted then to deform.In contrast, in the first embodiment, using Japanese Zeon Co., Ltds SX9172 as
The adhesive of negative pole, it is suppressed that the deformation produced by overheat.
Fig. 3 shows the 1C discharge capacities in sixth embodiment and first embodiment.From figure 3, it can be seen that this implementation
The secondary cell of example shows high power capacity.
The possibility applied in industry：
Secondary cell of the present utility model can realize high output and high power capacity, be suitable for large-scale battery etc..For example, this
The secondary cell of utility model can conduct, geothermal power generation, wind-power electricity generation, solar power generation, the shakiness such as water power and wave-activated power generation
The battery of fixed TRT.Secondary cell of the present utility model is equally applicable to the moving bodys such as electric vehicle.
Preferred embodiment of the present utility model is the foregoing is only, it is all at this not to limit the utility model
Any modifications, equivalent substitutions and improvements made within the spirit and principle of utility model etc., should be included in the utility model
Protection domain within.
Claims (9)
1. a kind of secondary cell, including：First electrode and the second electrode immediately below the first electrode, first electricity
Pole is parallel to each other with second electrode, it is characterised in that between the first electrode and second electrode provided with hole-conductive layer and from
The upper and lower surface of sub- conducting shell, the hole-conductive layer and ion conducting layer is contacted with first electrode and second electrode respectively.
2. secondary cell as claimed in claim 1, it is characterised in that uniform intervals are placed with logical in the hole-conductive layer
In hole, the through hole ion conducting layer is formed filled with ion-conductive material.
3. secondary cell as claimed in claim 2, it is characterised in that the top surface of the first electrode is provided with the first colelctor electrode,
The top surface of the second electrode is provided with the second colelctor electrode.
4. the secondary cell as described in any one of claims 1 to 3, it is characterised in that partly led provided with p-type in the first electrode
Body.
5. the secondary cell as described in any one of claims 1 to 3, it is characterised in that the top surface of the hole-conductive layer and bottom
Face is equipped with electrolyte layers, and the electrolyte layers are covered in shape on the surface of the hole-conductive layer by electrolyte or solid electrolyte
Into.
6. the secondary cell as described in any one of claims 1 to 3, it is characterised in that the hole-conductive layer is by titanium oxide, silicon
Or ceramic material is made.
7. secondary cell as claimed in claim 2 or claim 3, it is characterised in that the thickness range of the hole-conductive layer is 6 μm
~25 μm.
8. secondary cell as claimed in claim 3, it is characterised in that first colelctor electrode and the second colelctor electrode are by stainless
Steel is made.
9. the secondary cell as described in any one of claims 1 to 3, it is characterised in that the first electrode and second electrode
Outer surface is coated with aluminum plastic film.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210305626A1 (en) * | 2020-03-25 | 2021-09-30 | Power Iv, Inc. | Secondary battery |
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2016
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210305626A1 (en) * | 2020-03-25 | 2021-09-30 | Power Iv, Inc. | Secondary battery |
| US11777144B2 (en) * | 2020-03-25 | 2023-10-03 | Power Iv, Inc. | Secondary battery |
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