CN109301138A - One kind is using lithium ion solid electrolyte piece as diaphragm button lithium battery and preparation method - Google Patents
One kind is using lithium ion solid electrolyte piece as diaphragm button lithium battery and preparation method Download PDFInfo
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- CN109301138A CN109301138A CN201811137435.5A CN201811137435A CN109301138A CN 109301138 A CN109301138 A CN 109301138A CN 201811137435 A CN201811137435 A CN 201811137435A CN 109301138 A CN109301138 A CN 109301138A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
For one kind of the invention using lithium ion solid electrolyte piece as diaphragm button lithium battery and preparation method, battery includes lithium ion solid electrolyte piece, positive plate, anode cover, lithium piece, negative electrode casing, electrolyte LiPF6, filter paper, stainless steel substrates and elastic slice.Preparation method are as follows: stoichiometrically raw material is weighed, takes raw material Li2CO3、SrCO3、ZrO2And Nb2O5It after mixing and ball milling, is ground to levigate after wet feed is dried, thin siccative is put into alumina crucible, and is put in chamber type electric resistance furnace, be warming up to 1100 DEG C and keep the temperature 10 hours and calcine, cooled down after decomposing carbonate sufficiently；After grinding tabletting obtains lithium ion solid electrolyte piece diaphragm sample, cooling, generation lithium ion solid electrolyte piece after solid phase synthesis is carried out, carries out cell apparatus after preparing positive plate, finished product is made in encapsulation.The lithium-ion electrolyte piece ionic conductivity is high, and electronic conductivity is low, and consistency is high, and Li dendrite is not easy to pierce through, and lithium battery good cycle is made.
Description
Technical field
The present invention relates to solid electrolytes and electrochemical field, suitable for using lithium ion solid electrolyte piece as the button of diaphragm
Battery is detained, more particularly to one kind using lithium ion solid electrolyte piece as diaphragm button lithium battery and preparation method.
Background technique
Lithium battery is the energy storage device being widely used at present, with height ratio capacity, long circulation life, memory-less effect
Characteristic, and have many advantages, such as safe and reliable and energy fast charging and discharging, the concern of vast researcher has been obtained, has been new energy
The hot spot of area research.Lithium battery is usually by being formed with lower component: positive electrode, negative electrode material, electrolyte, diaphragm and electricity
The composition such as pond shell.The main effect of the diaphragm of lithium battery be isolation positive and negative anodes make electronics can not by prevent short circuit,
In addition charge and discharge process can be carried out by lithium ion.Diaphragm is mainly based on polyethylene and polypropylene, with lithium metal at present
For in cathode charging process, Li dendrite can pierce through diaphragm and cause battery short circuit, the danger of burning and explosion can be caused.So exploitation
A kind of cathode that can reduce lithium dendrite growth or the diaphragm for limiting Li dendrite puncture become the key for developing lithium battery.
Lithium ion solid electrolyte is used for preparing all-solid-state battery, it belongs to a kind of function ceramics.But
Be at present for, there is lithium ion conductivity is low and the big bottleneck of solid solid interface impedance for lithium ion solid electrolyte.Therefore, if
Being made into all-solid lithium-ion battery still will have a long way to go.However lithium ion solid electrolyte has stronger hardness
With certain mechanical performance, the puncture of Li dendrite can be prevented, therefore can be improved the security performance of lithium battery.Lithium ion battery
Solid electrolyte mainly include LISICON/Thio-LISICON, NASICON, garnet-type solid electrolyte, Ca-Ti ore type/
Anti-perovskite type solid electrolyte.Wherein carbuncle type and perovskite solid electrolyte receive the extensive concern of scholar.This
Two based solid electrolyte lithium ion conductivities can reach~10-4S·cm-1, close to the conductivity of liquid electrolyte.And
The electronic conductivity of solid electrolyte is extremely low, usually a ten thousandth of ionic conductivity.
The Li-Ion Conduction and Stability of that Bing Huang and Chang-An Wang are delivered
Perovskite Li3/8Sr7/16Hf1/4Ta3/4O3, it is solid that the lithium ion with perovskite structure has been synthesized using high temperature solid-state method
Body electrolyte, the lithium ion conductivity of solid electrolyte is 3.8 × 10 at 25 degrees Celsius-4S cm-1.By being prepared to electrolyte
Anode carries out cyclic voltammetry, and the solid electrolytic confrontation lithium metal is unstable as the result is shown, and in 1.4V, lithium ion can be embedding
Enter into electrolyte.
Summary of the invention
The purpose of the present invention is directed to problem of the prior art, provides one kind using lithium ion solid electrolyte piece as diaphragm button
Lithium battery and preparation method, the lithium battery is using lithium ion solid electrolyte piece as solid membrane, LiFePO4As anode, metal
Lithium adds LiPF as cathode, both ends6It reduces interface impedance, button cell is then equipped in glove box.The battery with
The speed of 0.2C carries out first charge-discharge, and capacity is 101.0mAh g-1.After carrying out 50 charge and discharge, capacity remains to protect
Hold 95% or more capacity.It all illustrates above, it, can using lithium ion solid electrolyte piece as the button cell function admirable of diaphragm
To be applied in lithium battery.
Using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof, more particularly to one kind
(LiFePO4/LiPF6/Li0.375Sr0.4375Zr0.25Nb0.75O3Solid electrolyte sheet/LiPF6/ Li) button cell, it is suitable for lithium two
Primary cell；It relates to a kind of method for replacing existing lithium ion battery separator and improvement and the growth for inhibiting Li dendrite；It adopts
There is high density with lithium ion solid electrolyte piece prepared by the method for high temperature process heat, it is high-intensitive；The anode of lithium battery is adopted
Use LiFePO4, cathode is using metal lithium sheet, and electrolyte is using LiPF6.It is equipped in glove box, it is multiple with the speed of 0.2C
Charge and discharge remain to that lithium battery is made to have excellent chemical property, and at least can be with charge and discharge 300 times or more.
For one kind of the invention using lithium ion solid electrolyte piece as diaphragm button lithium battery, component includes lithium ion solid
Electrolyte sheet, positive plate, anode cover, lithium piece, negative electrode casing, electrolyte LiPF6, filter paper, stainless steel substrates and elastic slice, the lithium
Ion solid electrolyte sheet is sintered Li0.375Sr0.4375Zr0.25Nb0.75O3Potsherd.
The lithium ion solid electrolyte piece diameter is 16mm, with a thickness of 0.3mm.It is acted on and commercialized diaphragm phase
Together.The lithium ion solid electrolyte piece is used as diaphragm.
The positive plate is by LiFePO4, aluminium foil, PVDF solution and acetylene black is prepared, wherein in mass ratio
LiFePO4: PVDF solution: acetylene black=8:20:1.
The PVDF solution is that 1:19 mixed preparing forms with NMP example in mass ratio by PVDF binder.
The diameter of the positive plate is 13mm, and anode is with a thickness of 100 μm.
The lithium piece is negative electrode tab.
The lithium piece and electrolyte LiPF6It is commercially produced product.Wherein the diameter of lithium piece is 16mm, with a thickness of 1mm.
The filter paper is common qualitative filter paper, a diameter of 18mm, with a thickness of 1mm, for storing in the battery
Electrolyte LiPF6。
The anode cover, negative electrode casing, stainless steel substrates, elastic slice model CR2032, apparent size is diameter 20mm, thick
Degree is 3.2mm.
It is of the invention using lithium ion solid electrolyte piece as the button lithium battery of diaphragm, which is 25
DEG C, the discharge capacity of button cell is up to 101.0mAh g for the first time-1, capacity still has 87.9mAh g after 300 times-1, Ke Yizuo
For electric energy storing device.
It is a kind of using lithium ion solid electrolyte piece as the preparation method of the button lithium battery of diaphragm, including following step
It is rapid:
Step 1, prepared by lithium ion solid electrolyte piece:
(1) according to Li0.375Sr0.4375Zr0.25Nb0.75O3Stoichiometry raw material is weighed, take raw material Li2CO3、
SrCO3、ZrO2、Nb2O5, 0.45:0.4375:0.25:0.75 is mixed in molar ratio, ball milling, forms wet feed；
(2) wet feed is poured into glass culture dish, is covered, drying forms siccative, siccative is ground to levigate, is formed thin
Siccative；Wherein, the drying temperature is 120 DEG C, and drying time 2 is h；
(3) thin siccative is put into alumina crucible, and be put in chamber type electric resistance furnace, be warming up to 1100 DEG C and heat preservation 10 is small
When calcine, it is cooling after decomposing carbonate sufficiently；
(4) until after levigate, tabletting obtains lithium ion solid electrolyte piece diaphragm for calcined material grinding
Li0.375Sr0.4375Zr0.25Nb0.75O3Sample；
(5) sample carries out cooling, generation Li after solid phase synthesis0.375Sr0.4375Zr0.25Nb0.75O3Potsherd；As lithium
Ion solid electrolyte sheet；Wherein, the solid phase synthesis temperature is 1250 DEG C, soaking time 10h；
Step 2, prepared by positive plate:
(1) in mass ratio, LiFePO4: PVDF solution: acetylene black=8:20:1 is applied to metallic aluminium after mixing raw material
On foil, pole coating is formed；
(2) coated pole coating is cut into entelechy piece after being dried, and compacting is used as positive plate；
Step 3, cell apparatus:
It is sequentially placed anode cover, positive plate is soaked with LiPF6Filter paper, Li0.375Sr0.4375Zr0.25Nb0.75O3Potsherd,
It is soaked with LiPF6Filter paper, negative electrode tab and stainless steel substrates, elastic slice and negative electrode casing, encapsulation is made with lithium ion solid electrolyte piece
For the button lithium battery of diaphragm.
In the step 1 (1), raw material Li2CO3、SrCO3、ZrO2And Nb2O5By drying and processing, to remove in raw material
Moisture, be convenient for accurately weighing, drying course is to be dried 5 hours in air dry oven with 150 DEG C.
In the step 1 (1), Li2CO3It is used to compensate the volatilization under high temperature including 20% in proportion.
In the step 1 (1), ball milling operation carries out in a planetary ball mill, detailed process are as follows: is put into raw material poly-
In urethane ball grinder, with alcohol smell dispersing agent, zirconia ball is ball-milling medium, then by ball grinder be put into planetary ball mill with
The revolving speed ball milling of 300r/min 12 hours.
In the step 1 (2), drying operation carries out in air dry oven, and siccative grinding operation is in the agate mortar
It carries out.
In the step 1 (3), the temperature increasing schedule of chamber type electric resistance furnace be room temperature to the time used in 300 DEG C be 50min, 300
DEG C to the time used in 1000 DEG C be 90min, the time used in 1000 DEG C to 1100 DEG C is 50min, and the type of cooling is cold with furnace
But.
In the step 1 (4), calcined material, which is put into agate mortar, to be ground.
It in the step 1 (4), uses and diameter is used to carry out tabletting for the stainless steel mould of 20mm, pressure 6MPa is obtained
The diameter for obtaining sample is 20mm, thickness 1mm.
In the step 1 (5), sample is placed on alumina plate, and cover sample using calcined female powder,
Solid phase synthesis carries out in chamber type electric resistance furnace, and the temperature increasing schedule of the chamber type electric resistance furnace is room temperature to 300 DEG C of institute's used times
Between be 50min, the time used in 300 DEG C to 1000 DEG C be 90min, the time used in 1000 DEG C to 1250 DEG C be 125min, it is cold
But mode is furnace cooling.
In the step 1 (5), the lithium ion solid electrolyte piece of preparation, through detecting, lithium ion solid electrolyte piece
Lithium ion conductivity is 1.23 × 10-5S·cm-1, the electronic conductivity of lithium ion solid electrolyte piece is 1.15 × 10-8S·
cm-1。
In the step 1 (5), detection process are as follows: Li0.375Sr0.4375Zr0.25Nb0.75O3Potsherd both sides coat gold paste,
As blocking electrode, coated potsherd is placed in resistance furnace and dries 2 hours for 700 DEG C, and the organic matter in gold paste is divided completely
Solution tests AC impedance using electrochemical workstation, obtains the lithium ion conductance of lithium ion solid electrolyte piece according to formula (1)
Rate is 1.23 × 10-5S·cm-1, the electronics of lithium ion solid electrolyte piece is obtained using chronoamperometry and according to formula (2)
Conductivity is 1.15 × 10-8S·cm-1, in which:
The formula (1) is σ=L/ (RA)；
In formula: σ is the lithium ion conductivity (Scm of lithium ion solid electrolyte piece-1)；L is lithium ion solid electrolyte
The thickness (cm) of piece；R is AC impedance (Ω)；A is the area of a circle (cm of lithium ion solid electrolyte piece2)。
The formula (2) is σe=(IL)/(UA)
In formula: σeFor the electronic conductivity (Scm of lithium ion solid electrolyte piece-1)；L is lithium ion solid electrolyte piece
Thickness (cm)；R is AC impedance (Ω)；A is the area of a circle (cm of lithium ion solid electrolyte piece2)；I is chrono-amperometric
Stabling current (A)；U is the application voltage (V) of chronoamperometry.
In the step 2 (2), pole coating is placed in a vacuum drying oven, 80 DEG C of vacuum heat-preserving diels are done
It is dry.
In the step 2 (2), the coating after drying is cut into entelechy piece using slicer, and the entelechy piece diameter is
13mm, with a thickness of 100 μm.
In the step 2 (2), entelechy piece, pressure 10MPa are compacted using tablet press machine.
In the step 3, the negative electrode tab is the lithium piece of compacting.
In the step 3, charge-discharge test is carried out to by the button lithium battery of diaphragm of lithium ion solid electrolyte piece,
Charge/discharge speed is 0.2C, and charge and discharge reach 300 times or more.
Beneficial effects of the present invention:
1, of the invention using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof, lithium-ion electric
It is high to solve matter piece ionic conductivity, electronic conductivity is low, and consistency is high, suitable for lithium battery.
2, Li of the invention0.375Sr0.4375Zr0.25Nb0.75O3Lithium ion solid electrolyte piece high mechanical strength, Li dendrite is not
It easily pierces through, can replace existing lithium-ion membrane and use.
3, Li of the invention0.375Sr0.4375Zr0.25Nb0.75O3Lithium ion solid electrolyte piece is provided in lithium battery, circulation
Performance is good, at least can be with charge and discharge 300 times or more.
Detailed description of the invention
Fig. 1 is the preparation of the embodiment of the present invention 1 using lithium ion solid electrolyte piece as half electricity in the button lithium battery of diaphragm
Pond sectional view, in which: 1-1 is negative electrode casing；1-2 is elastic slice；1-3 is stainless steel substrates；1-4 is metal lithium sheet；1-5 is to be soaked with electrolysis
The filter paper of liquid；1-6 is lithium ion solid electrolyte piece；1-7 is positive plate；1-8 is anode cover；
Fig. 2 is the preparation of the embodiment of the present invention 1 using lithium ion solid electrolyte piece as the charge and discharge of the button lithium battery of diaphragm
Electric curve, in which: 2-1 is first lap charging and discharging curve, and 2-2 is the 100th circle charging and discharging curve, and 2-3 is that the 200th circle charge and discharge are bent
Line, 2-4 are the 300th circle charging and discharging curve.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
The lithium piece that embodiment uses, electrolyte LiPF6, LiFePO4, aluminium foil, PVDF binder, acetylene black, nmp solvent is equal
From commercially available；The model (LAND CT-2001A) of the cell tester of use；
Public affairs in following embodiment, in the electronic conductivity calculating of lithium ion conductivity and electrolyte sheet to electrolyte sheet
Formula (1) is σ=L/ (RA)；
In formula: σ is the lithium ion conductivity (Scm of solid electrolyte sheet-1)；L is the thickness (cm) of electrolyte sheet；R is
AC impedance (Ω)；A is the area of a circle (cm of electrolyte sheet2)。
Formula (2) is σe=(IL)/(UA)
In formula: σeFor the electronic conductivity (Scm of solid electrolyte sheet-1)；L is the thickness (cm) of electrolyte sheet；R is to hand over
Flow impedance value (Ω)；A is the area of a circle (cm of electrolyte sheet2)；I is the stabling current (A) of chrono-amperometric；U is chronoamperometry
Application voltage (V).
Embodiment 1
Of the invention is a kind of using lithium ion solid electrolyte piece as the button lithium battery of diaphragm, and half-cell sectional view is as schemed
Shown in 1,1-1 is negative electrode casing；1-2 is elastic slice；1-3 is stainless steel substrates；1-4 is lithium piece；1-5 is the filter paper for being soaked with electrolyte；
1-6 is lithium ion solid electrolyte piece；1-7 is positive plate；1-8 is anode cover, and the lithium ion solid electrolyte piece is to burn
Li after knot0.375Sr0.4375Zr0.25Nb0.75O3Potsherd；
It includes component are as follows: lithium ion solid electrolyte piece 1-6, positive plate (LiFePO4, aluminium foil, PVDF binder, second
Acetylene black, nmp solvent) 1-7, anode cover 1-8, lithium piece 1-4, negative electrode casing 1-1, electrolyte LiPF6, filter paper 1-5, stainless steel substrates 1-
3 and elastic slice 1-2, the lithium ion solid electrolyte piece be sintered Li0.375Sr0.4375Zr0.25Nb0.75O3Potsherd；
The model CR2032 of the anode cover 1-8, negative electrode casing 1-1, stainless steel substrates 1-3, elastic slice 1-2, apparent size
For diameter 20mm, with a thickness of 3.2mm；
The positive plate 1-7 is by commercially produced product LiFePO4, aluminium foil, PVDF binder, acetylene black, NMP preparation, matter
Amount compares LiFePO4: PVDF (is dissolved in NMP, the mass ratio of PVDF and NMP are 1:19): acetylene black=8:20:1, positive plate
The diameter of 1-7 is 13mm, and anode is with a thickness of 100 μm；
The diameter of the lithium piece 1-4 is 16mm, with a thickness of 1mm；
The filter paper 1-5 is common qualitative filter paper, and a diameter of 18mm, with a thickness of 1mm, effect is in battery
Middle storage electrolyte LiPF6；
The material of the lithium ion solid electrolyte piece 1-6 is sintered Li0.375Sr0.4375Zr0.25Nb0.75O3Ceramics
Piece, diameter 16mm, with a thickness of 0.3mm.
Of the invention a kind of using lithium ion solid electrolyte piece as the button lithium battery of diaphragm, button cell operating temperature
It is 25 DEG C, the discharge capacity of button cell is up to 101.0mAh g for the first time-1, capacity still has 87.9mAh g after 300 times-1, can
Using as electric energy storing device.
It is above-mentioned using lithium ion solid electrolyte piece as the preparation method of the button lithium battery of diaphragm, including following step
It is rapid:
(1) in preparation Li0.375Sr0.4375Zr0.25Nb0.75O3Before potsherd, by raw material Li2CO3、SrCO3、ZrO2With
Nb2O5It is dried 5 hours in air dry oven with 150 DEG C, removes the moisture in raw material, be convenient for accurately weighing；
(2) according to Li0.375Sr0.4375Zr0.25Nb0.75O3Stoichiometry raw material is weighed, wherein will be additional it is more
20% lithium carbonate is added for compensating the volatilization under high temperature, 0.45:0.4375:0.25:0.75, weighs and remove water in molar ratio
The raw material Li divided2CO3、SrCO3、ZrO2And Nb2O5；
(3) raw material will be weighed up to be put into polyurethane ball-milling pot, with alcohol smell dispersing agent, and zirconia ball is ball-milling medium,
Ball grinder is put into planetary ball mill with the revolving speed ball milling of 300r/min 12 hours again；
(4) ball after ball milling by wet feed together with zirconium oxide pours into glass culture dish, covers, in air dry oven with
120 DEG C dry 2 hours, and siccative is put into agate mortar and grinds until levigate；
(5) thin siccative is put into alumina crucible and cover alumina cover (entrance for avoiding other impurities) be put in it is box
Calcined in resistance furnace, be warming up to 1100 DEG C and keep the temperature decomposes carbonate sufficiently within 10 hours after cool down, wherein chamber type electric resistance furnace
Temperature increasing schedule be room temperature to the time used in 300 DEG C be 50min, the time used in 300 DEG C to 1000 DEG C is 90min, and 1000 DEG C are arrived
It is furnace cooling that time used in 1100 DEG C, which is the 50min type of cooling,；
(6) calcined material is put into grinding in agate mortar until levigate, the stainless steel for the use of diameter being then 20mm
Mold carries out tabletting, and pressure 6MPa, obtained sample diameter is 20mm, with a thickness of 1mm；
(7) sample is covered using calcined female powder on alumina plate, is subsequently placed in chamber type electric resistance furnace and is warming up to
It 1250 DEG C and keeps the temperature cooling after 10 hours progresss solid phase synthesis, wherein the temperature increasing schedule of chamber type electric resistance furnace is room temperature to 300
Time used in DEG C is 50min, and the time used in 300 DEG C to 1000 DEG C is 90min, and the time used in 1000 DEG C to 1250 DEG C is
125min, the type of cooling are furnace cooling；
(8)Li0.375Sr0.4375Zr0.25Nb0.75O3Potsherd both sides coat gold paste as blocking electrode, coated sample
It is placed in resistance furnace and dries 2 hours for 700 DEG C, the organic matter in gold paste is decomposed completely, tested and exchanged using electrochemical workstation
Impedance is 1.23 × 10 according to the lithium ion conductivity that formula (1) obtains electrolyte sheet-5S·cm-1, simultaneously using chronoamperometry
It is 1.15 × 10 according to the electronic conductivity that formula (2) obtains electrolyte sheet-8S·cm-1；
(9)LiFePO4Anode pole piece coating: LiFePO4: PVDF solution: the mass ratio of acetylene black is 8:20:1, uses painting
On cloth machine automatic coating to metal aluminum foil；
(10) coated pole coating is placed in a vacuum drying oven, 80 DEG C of vacuum heat-preserving diels；
(11) it is 13mm that coating after being dried in vacuo, which is cut into diameter using slicer, anode with a thickness of 100 μm of entelechy piece,
Entelechy piece, pressure 10MPa are compacted using tablet press machine；
(12) battery is equipped in glove box: being sequentially placed anode cover 1-8 with tweezers, positive plate 1-7 is soaked with LiPF6Filter
The scraps of paper 1-5, Li0.375Sr0.4375Zr0.25Nb0.75O3Potsherd is soaked with LiPF6Filter paper 1-5, the lithium piece 1-4 of compacting and stainless
Steel disc 1-3, elastic slice 1-2 and negative electrode casing 1-1 encapsulate assembled button cell with sealing machine；
(13) using cell tester to it is assembled using lithium ion solid electrolyte piece as the button lithium battery of diaphragm into
Row charge-discharge test, charge/discharge speed 0.2C, charging and discharging curve are as shown in Figure 2, in which: 2-1 is that first lap charge and discharge are bent
Line, 2-2 are the 100th circle charging and discharging curve, and 2-3 is the 200th circle charging and discharging curve, and 2-4 is the 300th circle charging and discharging curve, charge and discharge
Electric speed is 0.2C.
Claims (4)
1. one kind is using lithium ion solid electrolyte piece as diaphragm button lithium battery, which is characterized in that be electrolysed including lithium ion solid
Matter piece, positive plate, anode cover, lithium piece, negative electrode casing, electrolyte LiPF6, filter paper, stainless steel substrates and elastic slice, the lithium ion
Solid electrolyte sheet is sintered Li0.375Sr0.4375Zr0.25Nb0.75O3Potsherd.
2. according to claim 1 using lithium ion solid electrolyte piece as diaphragm button lithium battery, which is characterized in that described
Lithium ion solid electrolyte piece lithium ion conductivity be 1.23 × 10-5S·cm-1, the electronics of lithium ion solid electrolyte piece
Conductivity is 1.15 × 10-8S·cm-1。
3. described in claim 1 using lithium ion solid electrolyte piece as the preparation method of diaphragm button lithium battery, feature exists
In, including the following steps:
Step 1, prepared by lithium ion solid electrolyte piece:
(1) according to Li0.375Sr0.4375Zr0.25Nb0.75O3Stoichiometry raw material is weighed, take raw material Li2CO3、SrCO3、
ZrO2And Nb2O5, 0.45:0.4375:0.25:0.75 is mixed in molar ratio, ball milling, forms wet feed, wherein add 20wt%'s
Lithium carbonate makes up the volatilization of elemental lithium in pyroprocess into raw material；
(2) wet feed is poured into glass culture dish, is covered, drying forms siccative, siccative is ground to levigate, is formed thin dry
Material；Wherein, the drying temperature is 120 DEG C, and drying time 2 is h；
(3) thin siccative is put into alumina crucible, and be put in chamber type electric resistance furnace, be warming up to 1100 DEG C and keep the temperature 10 hours and forge
It burns, it is cooling after decomposing carbonate sufficiently；
(4) until after levigate, tabletting obtains lithium ion solid electrolyte piece diaphragm 0.45:0.4375 for calcined material grinding:
0.25:0.75 sample；
(5) sample carries out cooling, generation Li after solid phase synthesis0.375Sr0.4375Zr0.25Nb0.75O3Potsherd, as lithium ion
Solid electrolyte sheet；Wherein, the solid phase synthesis temperature is 1250 DEG C, soaking time 10h；
Step 2, prepared by positive plate:
(1) in mass ratio, LiFePO4: PVDF solution: acetylene black=8:20:1 is applied on metal aluminum foil after mixing raw material,
Form pole coating；
(2) coated pole coating is cut into entelechy piece after being dried, and compacting is used as positive plate；
Step 3, cell apparatus:
It is sequentially placed anode cover, positive plate is soaked with LiPF6Filter paper, Li0.375Sr0.4375Zr0.25Nb0.75O3Potsherd is soaked with
LiPF6Filter paper, negative electrode tab and stainless steel substrates, elastic slice and negative electrode casing, encapsulation be made with lithium ion solid electrolyte piece be every
The button lithium battery of film.
4. it is according to claim 3 using lithium ion solid electrolyte piece as the preparation method of diaphragm button lithium battery, it is special
Sign is, in the step 3, carries out charge-discharge test to by the button lithium battery of diaphragm of lithium ion solid electrolyte piece,
Charge/discharge speed is 0.2C, and charge and discharge reach 300 times or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811137435.5A CN109301138B (en) | 2018-09-28 | 2018-09-28 | Button lithium battery taking lithium ion solid electrolyte sheet as diaphragm and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811137435.5A CN109301138B (en) | 2018-09-28 | 2018-09-28 | Button lithium battery taking lithium ion solid electrolyte sheet as diaphragm and preparation method |
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| CN110828756A (en) * | 2019-10-29 | 2020-02-21 | 东北大学 | Lithium ion solid electrolyte diaphragm and preparation and use methods thereof |
| CN110931689A (en) * | 2019-10-29 | 2020-03-27 | 东北大学 | Perovskite type lithium ion solid electrolyte diaphragm and preparation and use methods thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110828756A (en) * | 2019-10-29 | 2020-02-21 | 东北大学 | Lithium ion solid electrolyte diaphragm and preparation and use methods thereof |
| CN110931689A (en) * | 2019-10-29 | 2020-03-27 | 东北大学 | Perovskite type lithium ion solid electrolyte diaphragm and preparation and use methods thereof |
| CN110828756B (en) * | 2019-10-29 | 2021-07-23 | 东北大学 | Lithium ion solid electrolyte diaphragm and preparation and use methods thereof |
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