CN105098250B - A kind of positive plate is free of the lithium ion battery of lithium - Google Patents
A kind of positive plate is free of the lithium ion battery of lithium Download PDFInfo
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- CN105098250B CN105098250B CN201410192393.0A CN201410192393A CN105098250B CN 105098250 B CN105098250 B CN 105098250B CN 201410192393 A CN201410192393 A CN 201410192393A CN 105098250 B CN105098250 B CN 105098250B
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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
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Abstract
The invention discloses a kind of high capacity lithium ion battery that can be charged, there is no lithium ion in its positive electrode, the lithium carrier of battery be by cathode lithium metal or lithium compound provide.Positive electrode used in the anode of battery is common metal oxide or metal composite oxide, they can provide the up to theoretical capacity of 600mAh/g；Cathode corresponding with anode is Integral load pole piece in a cell of this invention, and this Integral load pole piece is to use not react the metal powder to form alloy, large capacity negative material such as Li with lithium metal in an inert atmosphere4.4It Si or Li and Si, metallic lithium powder and leads lithium ion additive material and selection and enhances support material using structure, made by the method for roll-in made membrane, the theoretical capacity of up to 2100 mAh/g can be provided.
Description
Technical field
The present invention relates to a kind of production methods of lithium ion battery of positive plate without lithium.
Background technology
Other than the currently commercially disposable lithium cell in addition to making cathode with lithium metal, the anode of other rechargeable lithium batteries is all
It is the composite metal oxide material containing lithium, corresponding negative material is usually graphite and Li4Ti5O12.Such battery
Usually use LiCoO2、LiMn2O4、LiNimColMnnO2、 LiNimColAlnO2（m+l+n=1）、LiFePO4、LiNimMnnO2（m+n
=1）、LiNi1.5Mn0.5O4Etc. lithium metals composite oxides make positive electrode, these materials can usually be provided less than 180mAh/g
Stabilization active volume.From electrochemical theory, as long as the material that anode is oxidizing, as long as cathode, which has, can restore these
The reducing agent of oxidant, and have suitable electrolyte solution transmit the anion ferried between a positive electrode and a negative electrode or sun from
Son, so that it may with construct can be with the battery of charge and discharge.For if electronics and lithium can be provided with the lithium battery cathode of charge and discharge
Ion, and anode is the oxidant that can be reduced, and being embedded in by lithium ion, so that it may with construct can be with charge and discharge
Lithium battery.The capacity of such lithium battery is no longer limited by the lithium concentration of anode, and simple metal can be selected to aoxidize
Object is positive electrode, such as NiO2、CoO2、FeVO4、NiVO4、CoVO4、V2O5、MnO2、KMnO4、Fe2O3、Cr2O3、CeO2、MoO3Deng
And mixed-metal oxides make positive electrode, the unit Coulomb capacity of material can be higher than 500mAh/g.
Invention content
The present invention provides a kind of lithium ion battery of the positive plate without lithium, and production method includes：A1), one kind is made not
Battery anode slice containing lithium；A2 a kind of battery cathode sheet containing lithium), is made；A3), without lithium battery anode slice, contain lithium
Battery cathode sheet, diaphragm and electrolyte solution be assembled into lithium ion battery.
The present invention battery be by without lithium anode, enough lithium ions and electronics can be provided cathode, diaphragm with
And electrolyte solution assembles, assemble method with it is existing can be identical with the business lithium battery of charge and discharge.
Common LiPF can be used in the electrolyte solution of the used in battery of the present invention6It is dissolved in the molten of carbonic ester lithium preparation
Liquid.
Preferably, the battery anode slice is made of the raw material without lithium, the raw material without lithium includes gold
Belong to oxide active material and auxiliary agent.
As further preferred, the raw material without lithium is NiO2、CoO2、FeVO4、NiVO4、CoVO4、V2O5、MnO2、
KMnO4、Fe2O3、TiO2、Co2O3、Sb2O5、Bi2O5、Ni2O3、Cr2O3、CeO2、MoO3、NaOH、Na2O、KOH、K2O、MgO、CaO、
SrO、BaO、Mg(OH)2、Ca(OH)2、Sr(OH)2、Ba(OH)2、B2O3、Al2O3、Ga2O3、In2O3、SnO、Sb2O3、Bi2O3、
SnO2、PbO、PbO2、ZrO2、Nb2O5、MoO3、WO3、Y2O3、Nd2O3、Eu2O3、Gd2O3、Tb2O3、Pm2O3、Pr2O3、Ho2O3、
Er2O3、Tm2O3、Lu2O3、Pm2O3、Yb2O3And La2O3At least one of and/or the raw material without lithium in contain to
The metal composite oxide of few two kinds of metallic elements composition.
For the raw material without lithium mainly by two kinds at being grouped as, one of which ingredient is mainly to play redox in the present invention
It includes the higher metal oxide active material of oxidation-reduction potential that effect, which generates the oxide that different oxidation state are appraised at the current rate, is activity
Metal oxide.Another component is auxiliary agent, including the lower metal oxide of oxidation-reduction potential and hydroxide addition
Agent, auxiliary agent are the metal oxide components of modified electrode material object performance, their addition can greatly improve filling for battery
Discharge performance.
The raw material without lithium be include the higher metal oxide active material of oxidation-reduction potential, redox electricity
What the lower metal oxide in position and hydroxide additive were combined according to a certain percentage, specific complex method can
It is prepared in the method for selecting metal oxide directly to mix then roasting, corresponding metal salt solution presoma point can also be utilized
Prepared by the method that solution generates corresponding metal composite oxide, be not limited to both preparation methods here.
Preferably, the metal oxide active material is NiO2、CoO2、FeVO4、NiVO4、CoVO4、V2O5、MnO2、
KMnO4、Fe2O3、TiO2、Co2O3、Sb2O5、Bi2O5、Ni2O3、Cr2O3、CeO2And MoO3At least one of and/or the gold
Belong to the metal composite oxide of at least two metallic elements composition contained in oxide active material.The present invention is not restricted to these
The higher metal oxide active material of oxidation-reduction potential.
Preferably, the metal oxide active material is NiO2、CoO2、FeVO4、NiVO4、CoVO4、V2O5、MnO2、
KMnO4、TiO2And MoO3At least one of and/or the NiO2、CoO2、FeVO4、NiVO4、CoVO4、V2O5、MnO2、
KMnO4、TiO2And MoO3In contain at least two metallic elements composition metal composite oxide.
Preferably, the metal oxide active material is NiO2、CoO2、FeVO4、NiVO4、CoVO4、V2O5、MnO2With
And MoO3At least one of and/or the NiO2、CoO2、FeVO4、NiVO4、CoVO4、V2O5、MnO2And MoO3In contain
The metal composite oxide of at least two metallic elements composition.
Preferably, the auxiliary agent is metal oxide and/or metal hydroxides.
Preferably, the auxiliary agent is NaOH, Na2O、KOH、K2O、MgO、CaO、SrO、BaO、Mg(OH)2、Ca(OH)2、
Sr(OH)2、Ba(OH)2、B2O3、Al2O3、Ga2O3、In2O3、SnO、Sb2O3、Bi2O3、SnO2、PbO、PbO2、ZrO2、Nb2O5、
MoO3、WO3、Y2O3、Nd2O3、Eu2O3、Gd2O3、Tb2O3、Pm2O3、Pr2O3、Ho2O3、Er2O3、Tm2O3、Lu2O3、Pm2O3、Yb2O3
And La2O3At least one of and/or the auxiliary agent in contain at least two metallic elements composition metal composite oxide.
Preferably, the raw material without lithium further includes conductive carbon material.
The conductive carbon material includes conductive carbon black, conductive carbon nanotube etc.（Here both are not limited to）.
Preferably, the raw material without lithium further includes binder.
Preferably, the raw material without lithium further includes solvent.
The present invention also provides the production methods about positive plate in above-mentioned lithium ion battery of the anode without lithium, it includes will
The raw material mixing without lithium, is then coated on collector, and process is simultaneously dried and then suppressed up to the positive plate.
Preferably, the collector is Al collectors.
Further, the production method about negative plate, institute in above-mentioned lithium ion battery of the anode without lithium are also provided
The production method for stating negative plate comprises the following steps that：A), powder mixture is made in mixed raw material powder；B), by step a)
Manufactured powder mixture is suppressed to obtain lithium battery cathode plate.
As further preferred, the raw material powder includes metal powder, negative material powder and lithium powder；The metal powder be not easy with
The lithium powder forms alloy.
The present invention mends lithium amount and determines according to actual needs.Because positive electrode does not use lithium-containing materials in battery of the present invention,
Therefore the capacity of lithium battery is no longer limited by the lithium concentration of anode, can not only widen the model that lithium ion anode uses material
It encloses, also substantially increases the electrical property of the rechargeable lithium ion batteries prepared using the positive electrode（It is specifically shown in implementation of the present invention
1 to 3 electric performance test result of example）.Lithium is made an addition in the present invention in the material feedstock powder for making cathode, it is gold to mend lithium material
Belong to lithium powder.Cathode preparation method of the present invention can charge and discharge battery particularly useful for making the lithium ion prepared without lithium anode material
Cathode：In the present invention, metal powder fills the gap between large capacity negative material particle as possible under pressure, realizes metal
To the cladding of large capacity negative material particle；On the other hand, since metal has different degrees of elasticity, after removing the pressure all
It can partly spring back, so will produce small gap between metal and large capacity negative material particle.These gaps are on the one hand
Micro electrolyte solution can be allowed to enter to form Li+Access way, on the other hand these gaps are that lithium ion passes in and out large capacity
The volume change that negative material particle generates provides tolerance space, is conducive to the structure for stablizing battery cathode sheet.In addition, in anode
When material is free of lithium ion, cathode can provide enough lithium ions to ensure the high power capacity of realization battery；In addition, due to using
Metal is suppressed together with large capacity negative electrode active material can ensure that negative plate has excellent electric conductivity, integration of the invention
Battery cathode sheet need not use adhesive, can further improve the electric conductivity of negative plate；Finally, negative electrode active material is played
The metal powder of cladding and supporting function also plays collector, therefore the negative plate prepared using the method for the present invention after being pressed
Special collector is not needed.Negative plate of the present invention can provide for the anode of the invention lithium ion battery that not prepared by lithium-containing materials
Electronics and lithium ion, formed can charge and discharge lithium ion battery.
The metal powder for being not easy to form alloy with metal elemental lithium（Or particle）Filler and covering refer to metal
The small metal powder of lithium solubility in the metal powder, for example, Ni metal, Ag, Au, Ni, Co, Fe, Mn, Zn and they
Alloy and the alloyed powder of they and other metals and nonmetallic composition（Or particle）, but it is not limited to these types of metal material
Material.
Preferably, the raw material powder further includes leading lithium ion additive powder.
Preferably, the grain size of the metal powder is less than 100 microns.
Preferably, the grain size of the negative material powder is less than 20 microns.The grain size of large capacity negative material powder is less than 20
Micron can preferably realize the effect of the present invention.It is small for grain size when the grain size of large capacity negative material powder is less than 20 microns
It is more effective in the filling of 100 micron metal powder and cladding.
Preferably, the negative material powder is the negative electrode active material that capacity is more than 400mAh/g.
The large capacity negative material powder defined in the present invention is preferably the negative material that capacity is more than 400mAh/g, because
Metallic particles is used in the present invention（Or powder）Do the covering material of negative material, metallic particles can occupy segment space volume and again
Amount uses large capacity negative material effect relatively good in the present invention, therefore selects Fe3O4, silicon（Si）, Li-Si alloy, boron（B）、
Sn, SnO, black phosphorus, TiO2Or to do negative electrode active material more meaningful for the materials such as their composite materials for being mixed in a certain ratio,
But the present invention is not limited to these types of material or composite materials that they are mixed in a certain ratio.
Preferably, the negative material powder is Fe3O4Powder, silicon（Si）Powder, Li-Si Alloy Powder, boron（B）Powder, Sn powder, SnO
Powder, black phosphorus powder and TiO2At least one of powder.The large capacity negative material powder can be individually for Si powder, Li-Si alloy
Powder, B powder, Sn powder, Fe3O4Powder, Sn powder, SnO powder, TiO2Powder can also be Fe3O4Powder, silicon（Si）Powder, Li-Si Alloy Powder, boron（B）
Powder, Sn powder, SnO powder, black phosphorus powder and TiO2At least one of powder needs the mixed powder formed in proportion.
Preferably, the lithium powder diameter is less than 200 microns.Metallic lithium powder of the grain size less than 200 microns can be better
Realize the effect of the present invention.
Preferably, the metal powder is the metal of any metallic element in Cu, Ag, Au, Ni, Co, Fe, Mn and Zn
The metal powder of the alloy of the formation of at least two metallic elements in powder and/or described Cu, Ag, Au, Ni, Co, Fe, Mn and Zn.
Preferably, the metal powder is the metal powder of any metallic element and/or described Cu, Ag in Cu, Ag and Au
And in Au the alloy of the formation of at least two metallic elements metal powder.
As further preferred, the metal powder is Ni metal powder.
As further preferred, the metal powder is Cu-Zn alloyed powders.
Preferably, the lithium ion additive powder of leading is lithium ion conductor.
In the present invention in order to construct more lithium ion tunnel in negative plate, selection, which can enhance, leads lithium ion ability
Material do additive negative plate.
Preferably, the lithium ion additive powder of leading is carbon black, carbon nanotube, graphene, Li4Ti5O12、LiBO2、
Li3PO4、LinSi、Li2S、LimB and/or Li3N, wherein n=0.1~4, m=0.1~3.
Preferably, compacting described in step b), which is powder mixture described in direct roll-in in an inert atmosphere, is made pole
Then piece carries out the negative plate that lithium ion battery is made in laser scanning sintering to the pole piece in an inert atmosphere.
Preferably, compacting described in step b), which is powder mixture described in direct roll-in in an inert atmosphere, is made pole
Then piece carries out the cathode that lithium ion battery is made in plasma scan heating sintering to the pole piece in an inert atmosphere
Piece.
Preferably, the drawing method includes：
B1 step a)), is obtained into the powder mixture and is added to liquid do not reacted with lithium powder and that volatilization can be heated
It is uniformly mixed in dispersant and slurry is made；
B2), step b1) made of slurry be coated in structure enhancing support material, reheat volatilization and remove the liquid
Body dispersant obtains just pole piece, and just pole piece obtains the negative plate of lithium ion battery described in last roll-in.
In order to further enhance the intensity of negative plate, a kind of method of the invention is burnt to pole piece after suppressing pole piece
Knot processing, for example is done by sintering processes or pole piece is heated to approach cladding metal for pole piece with laser or plasma and is melted
It puts and carries out roll-in.Another method for improving pole piece intensity of the invention is negative electrode active material, metal powder, additive
And/or lithium powder is dispersed in structure enhancing support material, is such as dispersed in structure enhancing support material carbon cloth or net, macromolecule
Polymer cloth or net are not easy to be formed on the porous metals piece or metal mesh of alloy with lithium metal, then carry out roll-in.
For example the matched negative material of lithium anode material is free of needed for rechargeable lithium ion batteries of the present invention in order to realize
Production method selects the metal powder for being not easy that alloy is formed with lithium metal（Or particle）As filler and covering, carbon is selected
Fiber cloth or net, high molecular polymer cloth or net are not easy to form the porous metals piece of alloy or metal mesh with lithium metal to be knot
Structure enhances support material, and selection large capacity negative material is negative electrode active material, and it is that cathode mends lithium active material to select lithium metal
And it selects to enhance and leads the material of lithium ion ability and do additive negative plate.In the manufacturing process of negative plate, first
Metal powder, large capacity negative material powder, lithium powder and lead lithium ion additive addition liquid dispersant（Liquid dispersant be not with
The liquid compound of lithium powder reaction）In be uniformly mixed slurry is made, slurry be coated on structure enhancing support material on, then wave
Hair removal dispersant, pole piece is obtained by roll-in.In such negative plate, metal component ensure that the good conductive son of pole piece
Property, the electrolyte in gap between metal and large capacity negative material particle ensure that pole piece is good and lead lithium ion performance,
Structure enhancing support material ensure that the good mechanical structure stability of pole piece, so the integrated battery cathode sheet tool of the present invention
There is a good comprehensive performance, service life is than general battery cathode length of a film, the ratio energy of battery unit volume or Unit Weight
Density is higher than common lithium battery.
Preferably, the liquid dispersant is organic solution.
In the present invention, the liquid dispersant is the organic solvent that can be volatilized not reacted with lithium metal and is dissolved with
The organic solution of other components, for example be the hydrocarbon compound and ether compound of liquid at room temperature, the effect of dispersant is
Help being mutually mixed for each component powder of electrode processed that mixed uniformly slurry is made.
Preferably, the liquid dispersant is liquid hydrocarbon compound and/or liquid ether compound.
Preferably, at least one of ether, alkane, alkene and aromatic hydrocarbons that it is 7~20 that the liquid dispersant, which is carbon number,
Solution.
Preferably, the liquid dispersant is dissolved with the ether, alkane, alkene that mass fraction is 0.1%~20% paraffin
And at least one of aromatic hydrocarbons solution.
Preferably, the liquid dispersant is ethereal solution.
Preferably, the liquid dispersant is dissolved with the alkane solution that mass fraction is 0.1%~20% paraffin.
Preferably, the liquid dispersant is dissolved with the petroleum ether solution that mass fraction is 0.1%~20% paraffin.
Preferably, the structure enhancing support material is at least one in porous chips, porous membrane, woven fabric and knitmesh
Kind.
In the present invention, described structure enhancing support material is can to enhance the material of electrode slice intensity, general to select
Porous chips that target material is made, film, the cloth and net being made into can have good knot when suppressing negative plate with other materials
It closes, such as carbon cloth or net, high molecular polymer cloth or net are not easy to form porous metals piece, the foam of alloy with lithium metal
Metal or metal mesh etc. are to enhance the intensity of negative plate using these materials.
Preferably, the structure enhancing support material is porous carbon fiber cloth, carbon fibre web, the high score not reacted with lithium
Sub- polymer cloth, the high molecular polymer net not reacted with lithium, be not easy with lithium metal formed alloy porous metals piece, be not easy with
Lithium metal forms the foam metal of alloy and is not easy to form at least one of the metal mesh of alloy with lithium metal.
Preferably, the structure enhancing support material is aramid fabric or aramid fiber net.
Preferably, the structure enhancing support material is the more of any metallic element in Ni metal, Ag, Au and Zn
The porous membrane for the alloy that at least two metallic elements are formed in hole film and/or the Ni metal, Ag, Au and Zn.
Preferably, the structure enhancing support material is the more of any metallic element in Ni metal, Ag, Au and Zn
The porous web for the alloy that at least two metallic elements are formed in hole pattern and/or the Ni metal, Ag, Au and Zn.
Preferably, the structure enhancing support material is foam metal Cu, foam metal Ag, foam metal Au and bubble
At least one of foam metal Zn.
Preferably, the structure enhancing support material is at least two metallic element shapes in Ni metal, Ag, Au and Zn
At alloy foam metal piece.
The present invention makees the positive electrode of battery using simple metal oxide, and the capacity of battery is not in by positive electrode
The no limitation containing lithium ion, more flexible in terms of the selection of positive electrode and preparation, material is also easier to prepare, and is manufactured into
This is lower, it is easier to realize the manufacture of high capacity cell, for example use V2O5Do positive electrode, the theoretical capacity of positive electrode can be with
Reach 588mAh/g, uses MnO2Positive electrode is done, the theoretical capacity of positive electrode can reach 615mAh/g.In the positive electrode
In the battery of making, cathode is directly negative electrode active material, metal powder, the lithium of negative electrode active material cladding and supporting function
Powder, lead lithium ion additive or/and negative plate structure enhancing support material be pressed into negative plate method prepare Integral load
Pole, in this way, when positive electrode is the composite oxide of metal without Li ions, cathode can provide enough Li ions and ensure
Realize the high power capacity of battery.Further, since being suppressed together with large capacity negative electrode active material using metal, and need not use viscous
Mixture makes negative plate have excellent electric conductivity, so that the battery that the cathode coordinates positive electrode of the present invention to prepare is had good
Electrical property.Finally, the integrated battery cathode sheet of the present invention does not have to the electric conductivity that adhesive improves negative plate.
Description of the drawings
The electric performance test result figure of the 5th cycle of assembled battery prepared by Fig. 1 according to embodiments of the present invention 1；
The electric performance test result figure of the 5th cycle of assembled battery prepared by Fig. 2 according to embodiments of the present invention 2；
The electric performance test result figure of the 5th cycle of assembled battery prepared by Fig. 3 according to embodiments of the present invention 3.
Specific implementation mode
The cathode that the present invention prepares 1 to 3 embodiment of embodiment is prepared into button cell and carries out electric performance test, knob respectively
Detaining the specific preparation method of battery is：PVDF diaphragms are selected, electrolyte solution is the LiPF of 1.0 mol/L6Be dissolved in EMC/
EC/DC（1:1:1）In the mixed solvent, the operation preparation CR2025 button cells in glove box.
Embodiment 1：V2O5Anode is to Li-Si-Cu integration cathode
V2O5It is prepared by anode pole piece：Blended anode material V2O5（0.800 g）, conductive black（0.100 g）、PVDF
（0.100 g）And NMP（2.00 g）Slurry is prepared, pole piece processed on Al foils is coated on（Pole piece is 125 μm thick）, then dry, pole piece
The disk for being cut into 15mm uses, and is compacted at 2.0 MPa after blade.
It is prepared by cathode pole piece：In glove box under argon atmospher, the Li of 0.0300 g is weighed13Si4The copper powder of powder, 0.1200 g
It is uniformly mixed the tabletting in the mold of a diameter of 14.0mm（10.0 MPa）Negative plate processed, then with V2O5Positive plate assembled battery,
As shown in figure 1 and table 1, table 1 presses anode V to battery measurement result2O5Weight calculate charge/discharge capacity.
The electrical property measurement result of assembled battery prepared by table 1 according to embodiments of the present invention 1
Embodiment 2：V2O5Anode is to Li-Si-Cu integration cathode
V2O5It is prepared by anode pole piece：Blended anode material V2O5（0.800 g）, conductive black（0.100 g）、PVDF
（0.100 g）And NMP（2.00 g）Slurry is prepared, pole piece processed on Al foils is coated on（Pole piece is 125 μm thick）, then dry, pole piece
The disk for being cut into 15mm uses, and is compacted at 2.0 MPa after blade.
It is prepared by cathode pole piece：In glove box under argon atmospher, weigh the Cu powder of 0.0800 g, the lithium powder of 0.0100 g,
The silica flour of 0.0100 g, which is uniformly mixed, to be put into the foam Copper substrate that diameter is 14mm, the tabletting in the mold of a diameter of 14.0mm
（10.0 MPa）Negative plate processed, then with V2O5Positive plate assembled battery, battery measurement result is as shown in Fig. 2 and table 2, and table 2 is by just
Pole V2O5Weight calculate charge/discharge capacity.
Assembled battery electrical property measurement result prepared by table 2 according to embodiments of the present invention 2
Embodiment 3：V2O5Anode is to Li-Si-Cu integration cathode
V2O5It is prepared by anode pole piece：Blended anode material V2O5（0.800 g）, conductive black（0.100 g）、PVDF
（0.100 g）And NMP（2.00 g）Slurry is prepared, pole piece processed on Al foils is coated on（Pole piece is 125 μm thick）, then dry, pole piece
The disk for being cut into 15mm uses, and is compacted at 2.0 MPa after slice.
It is prepared by cathode pole piece：In glove box under argon atmospher, the Li of the Cu powder and 0.0200 g of 0.0800 g is weighed13Si4
Powder, which is uniformly mixed, to be put into the foam Copper substrate that diameter is 14mm, the tabletting in the mold of a diameter of 14.0mm（10.0 MPa）System is negative
Pole piece, then with V2O5Positive plate assembled battery, for battery measurement result as shown in Fig. 3 and table 3, table 3 presses anode V2O5Weight meter
Calculate charge/discharge capacity.
Assembled battery electrical property measurement result prepared by table 3 according to embodiments of the present invention 3
Claims (35)
1. a kind of positive plate is free of the lithium ion battery of lithium, production method includes：
A1 a kind of battery anode slice without lithium), is made；
A2 a kind of battery cathode sheet containing lithium), is made；
A3 the battery anode slice without lithium, the battery cathode sheet containing lithium, diaphragm and electrolyte solution), are assembled into lithium-ion electric
Pond；
The production method of the negative plate includes the following steps：
A), powder mixture is made in mixed raw material powder；
B) it, suppresses powder mixture made of step a) to obtain lithium battery cathode plate；The raw material powder includes metal powder, cathode
Material powder and lithium powder；The metal powder is not easy to form alloy with the lithium powder；The grain size of the metal powder is less than 100 microns；Institute
The grain size for stating negative material powder is less than 20 microns；
The battery anode slice is made of the raw material without lithium, and the raw material without lithium includes metal oxide active material
And auxiliary agent；The metal oxide active material is V2O5And/or MoO3；
The negative plate does not use adhesive.
2. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that the auxiliary agent is metal oxygen
Compound and/or metal hydroxides.
3. a kind of positive plate according to claim 2 be free of lithium lithium ion battery, which is characterized in that the auxiliary agent be NaOH,
Na2O、KOH、K2O、MgO、CaO、SrO、BaO、Mg(OH)2、Ca(OH)2、Sr(OH)2、Ba(OH)2、B2O3、Al2O3、Ga2O3、
In2O3、SnO、Sb2O3、Bi2O3、SnO2、PbO、PbO2、ZrO2、Nb2O5、WO3、Y2O3、Nd2O3、Eu2O3、Gd2O3、Tb2O3、
Pm2O3、Pr2O3、Ho2O3、Er2O3、Tm2O3、Lu2O3、Pm2O3、Yb2O3And La2O3At least one of and/or the auxiliary agent in
The multiple alloyed oxide of at least two metallic elements composition contained.
4. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that the raw material without lithium
It further include conductive carbon material.
5. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that the raw material without lithium
It further include binder.
6. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that the raw material without lithium
It further include solvent.
7. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium：It is characterized in that, the positive plate making side
Method include by described without lithium raw material mixing, be then coated on collector, and by drying then suppress up to it is described just
Pole piece.
8. a kind of positive plate according to claim 7 is free of the lithium ion battery of lithium, which is characterized in that the collector is Al
Collector.
9. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that the raw material powder also wraps
It includes and leads lithium ion additive powder.
10. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that the negative material powder
It is the negative electrode active material feed powder that capacity is more than 400mAh/g.
11. a kind of positive plate is free of the lithium ion battery of lithium according to claim 1, which is characterized in that the negative material
Powder is Fe3O4Powder, silicon (Si) powder, Li-Si Alloy Powder, boron (B) powder, Sn powder, SnO powder, black phosphorus powder and TiO2At least one in powder
Kind.
12. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that the grain size of the lithium powder
Less than 200 microns.
13. a kind of positive plate according to claim 1 be free of lithium lithium ion battery, which is characterized in that the metal powder be Cu,
The metal powder of any metallic element and/or described Cu, Ag, Au, Ni, Co, Fe, Mn in Ag, Au, Ni, Co, Fe, Mn and Zn
And the metal powder for the alloy that at least two metallic elements are formed in Zn.
14. a kind of positive plate according to claim 13 is free of the lithium ion battery of lithium, which is characterized in that the metal powder is
At least two metallic element shapes in the metal powder of any one metallic element and/or described Cu, Ag and Au in Cu, Ag and Au
At alloy metal powder.
15. a kind of positive plate according to claim 14 is free of the lithium ion battery of lithium, which is characterized in that the metal powder is Cu
Powder.
16. a kind of positive plate according to claim 14 is free of the lithium ion battery of lithium, which is characterized in that the metal powder is
Cu-Zn alloyed powders.
17. a kind of positive plate according to claim 9 is free of the lithium ion battery of lithium, which is characterized in that the lithium ion of leading adds
It is lithium ion conductor to add agent.
18. a kind of positive plate according to claim 17 is free of the lithium ion battery of lithium, which is characterized in that the lithium ion of leading adds
It is carbon black, carbon nanotube, graphene, Li to add agent4Ti5O12、LiBO2、Li3PO4、LinSi、Li2S、LimB and/or Li3N, wherein n
=0.1~4, m=0.1~3.
19. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that described in step b)
Compacting be powder mixture described in direct roll-in in an inert atmosphere be made pole piece, then in an inert atmosphere to the pole piece into
Negative plate is made in row laser scanning sintering.
20. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that described in step b)
Compacting be powder mixture described in direct roll-in in an inert atmosphere be made pole piece, then in an inert atmosphere to the pole piece into
Negative plate is made in row plasma scan heat-agglomerating.
21. a kind of positive plate according to claim 1 is free of the lithium ion battery of lithium, which is characterized in that pressed described in step b)
The method of system includes：
B1 step a)), is obtained into the powder mixture and is added to liquid dispersion do not reacted with lithium powder and that volatilization can be heated
It is uniformly mixed in agent and slurry is made；
B2), step b1) made of slurry be coated in structure enhancing support material, reheat volatilization and remove the liquid point
Powder obtains just pole piece, and first pole piece obtains negative plate described in last roll-in.
22. a kind of positive plate according to claim 21 is free of the lithium ion battery of lithium, which is characterized in that the liquid dispersant
For organic solution.
23. a kind of positive plate according to claim 22 is free of the lithium ion battery of lithium, which is characterized in that the liquid dispersant
For liquid hydrocarbon compound and/or liquid ether compound.
24. a kind of positive plate according to claim 23 is free of the lithium ion battery of lithium, which is characterized in that the liquid dispersant
At least one of ether, alkane, alkene and the aromatic hydrocarbons for being 7~20 for carbon number solution.
25. a kind of positive plate according to claim 24 is free of the lithium ion battery of lithium, which is characterized in that the liquid dispersant
For be 7~20 dissolved with the carbon number that mass fraction is 0.1%~20% paraffin ether, alkane, alkene and aromatic hydrocarbons at least one
The solution of kind.
26. a kind of positive plate according to claim 24 is free of the lithium ion battery of lithium, which is characterized in that the liquid dispersant
The ethereal solution for being 7~20 for carbon number.
27. a kind of positive plate according to claim 23 is free of the lithium ion battery of lithium, which is characterized in that the liquid dispersant
For dissolved with the alkane solution that mass fraction is 0.1%~20% paraffin.
28. a kind of positive plate according to claim 23 is free of the lithium ion battery of lithium, which is characterized in that the liquid dispersant
For dissolved with the petroleum ether solution that mass fraction is 0.1%~20% paraffin.
29. a kind of positive plate according to claim 21 is free of the lithium ion battery of lithium, which is characterized in that the structure enhancing branch
It is at least one of porous chips, porous membrane, woven fabric and knitmesh to hold material.
30. a kind of positive plate according to claim 21 is free of the lithium ion battery of lithium, which is characterized in that the structure enhancing branch
It is porous carbon fiber cloth, carbon fibre web, the high molecular polymer cloth not reacted with lithium, the polyphosphazene polymer not reacted with lithium to hold material
Object net is closed, is not easy to form the porous metals piece of alloy with lithium metal, is not easy to form the foam metal and not of alloy with lithium metal
At least one of the metal mesh of alloy is easily formed with lithium metal.
31. a kind of positive plate according to claim 30 is free of the lithium ion battery of lithium, which is characterized in that the structure enhancing branch
It is aramid fabric or aramid fiber net to hold material.
32. a kind of positive plate according to claim 29 is free of the lithium ion battery of lithium, which is characterized in that the structure enhancing branch
Hold material be Ni metal, the porous membrane of any metallic element and/or the Ni metal in Ag, Au and Zn, Ag, Au with
And the porous membrane for the alloy that at least two metallic elements are formed in Zn.
33. a kind of positive plate according to claim 30 is free of the lithium ion battery of lithium, which is characterized in that the structure enhancing branch
Hold material be Ni metal, the porous web of any metallic element and/or the Ni metal in Ag, Au and Zn, Ag, Au and
The porous web for the alloy that at least two metallic elements are formed in Zn.
34. a kind of positive plate according to claim 30 is free of the lithium ion battery of lithium, which is characterized in that the structure enhancing branch
It is at least one of foam metal Cu, foam metal Ag, foam metal Au and foam metal Zn to hold material.
35. a kind of positive plate according to claim 30 is free of the lithium ion battery of lithium, which is characterized in that the structure enhancing branch
Hold the foam metal piece that material is the alloy that at least two metallic elements are formed in Ni metal, Ag, Au and Zn.
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| CN107293701A (en) * | 2016-03-31 | 2017-10-24 | 比亚迪股份有限公司 | A kind of lithium ion battery anode active material and preparation method thereof, negative pole and the lithium ion battery comprising the negative pole |
| CN110429284B (en) * | 2019-07-01 | 2020-11-10 | 中山大学 | High-capacity and high-rate flexible zinc ion battery and application thereof |
| CN110277252B (en) * | 2019-07-03 | 2021-01-19 | 华南理工大学 | Tin antimony oxide/holmium oxide/indium tin oxide composite electrode material for supercapacitor and preparation method thereof |
| CN112820846A (en) * | 2019-11-15 | 2021-05-18 | 淮阴师范学院 | Manufacturing method of molybdenum lithium ion full battery |
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| CN102201565A (en) * | 2011-04-14 | 2011-09-28 | 杭州万好万家动力电池有限公司 | High-capacity metal lithium powder composite cathode and preparation method thereof, and multi-layer composite electrode |
| CN103647061A (en) * | 2013-11-15 | 2014-03-19 | 成都兴能新材料有限公司 | Preparation method of silicon-based alloy cathode material |
| CN103693690A (en) * | 2013-12-20 | 2014-04-02 | 武汉理工大学 | Porosity-controllable three-dimensional porous V2O5 hierarchical nanodisk, as well as preparation method and application thereof |
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| CN101425572B (en) * | 2007-10-29 | 2011-12-14 | 比亚迪股份有限公司 | Anode plate for lithium ionic cell and preparation thereof |
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| CN102201565A (en) * | 2011-04-14 | 2011-09-28 | 杭州万好万家动力电池有限公司 | High-capacity metal lithium powder composite cathode and preparation method thereof, and multi-layer composite electrode |
| CN103647061A (en) * | 2013-11-15 | 2014-03-19 | 成都兴能新材料有限公司 | Preparation method of silicon-based alloy cathode material |
| CN103693690A (en) * | 2013-12-20 | 2014-04-02 | 武汉理工大学 | Porosity-controllable three-dimensional porous V2O5 hierarchical nanodisk, as well as preparation method and application thereof |
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