CN113429199A - Sintering method of compact solid electrolyte LATP - Google Patents

Sintering method of compact solid electrolyte LATP Download PDF

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CN113429199A
CN113429199A CN202110816580.1A CN202110816580A CN113429199A CN 113429199 A CN113429199 A CN 113429199A CN 202110816580 A CN202110816580 A CN 202110816580A CN 113429199 A CN113429199 A CN 113429199A
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latp
wafer
powder
sintering
solid electrolyte
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索尔沃托瑞·格拉索
胡春峰
林勇
吴菁华
邓怀久
戴智权
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Southwest Jiaotong University
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Southwest Jiaotong University
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/95—Products characterised by their size, e.g. microceramics
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Abstract

The invention discloses a sintering method of compact solid electrolyte LATP, which comprises the following steps: taking 10g of LATP powder with the purity of more than 99 percent, and ball-milling for 12 hours by a planetary ball mill at the rotating speed of 300 rpm/min; taking out 0.2g of LATP powder, putting the LATP powder into a round die, and pressing the round die into a uniform wafer with certain strength under the uniaxial pressure of 300 MPa; and taking out the wafer, putting the wafer between two graphite felts with the size of 80 x 30 x 3mm, introducing a certain current voltage to two ends of the graphite felts, ensuring a certain sintering time, and then cooling to room temperature to obtain the required compact ceramic sample, wherein the argon flow is 50-250 ml/min. The method has simple operation and low requirement on equipment cost, and can prepare the LATP ceramic wafer in a large scale, and the prepared LATP ceramic wafer has higher density, complete and crack-free sample, smooth and flat surface, high relative density and high ionic conductivity.

Description

Sintering method of compact solid electrolyte LATP
Technical Field
The invention belongs to the technical field of preparation of solid electrolyte ceramic chips, and particularly relates to a sintering method of a compact solid electrolyte LATP.
Background
Compared with conventional liquid electrolytes, solid electrolytes have the advantages of low flammability, high thermal stability, no leakage, low explosion hazard, etc. [1 ]. More importantly, the solid electrolyte can effectively inhibit the growth of lithium dendrites due to excellent mechanical strength, and exerts the advantages of high energy density and power density of the lithium ion battery.
The performance of different electrolytes has large difference, and electrolytes with large research potential mainly comprise oxides, sulfides and polymer electrolytes. Among them, oxide electrolytes have been widely studied and have good stability in air, but have room temperature ionic conductivity inferior to sulfide electrolytes. The sulfide electrolyte has high lithium ion conductivity, can be used for preparing high-power batteries and high-temperature and low-temperature batteries, but has poor chemical stability. The polymer electrolyte has the advantages of high safety, light weight, large capacity and the like, and can be applied to flexible devices. The solid electrolyte used herein belongs to Li1.3Al0.3Ti1.7(PO4)3(LATP) oxide electrolyte, LATP having excellent stability in water and air [2]And the material source is wide, the manufacturing cost is low, the lithium ion conductivity is high, and the lithium ion battery has the necessary conditions for being applied to all-solid-state batteries. Currently, there are several methods for preparing LATP powders, mainly solid phase sintering [3]Coprecipitation method [4 ]]Sol-gel process [5 ]]The preparation method is simple and the process is relatively mature.
At present, the sintering methods for LATP electrolytes are mainly (1) conventional pressureless sintering techniques; (2) hot pressing sintering technology; (3) and (4) spark plasma sintering. The conventional pressureless sintering has a full heating rate, and usually needs heat preservation for several hours, and in the process, along with the growth of crystal grains, lithium element volatilizes, so that the ionic conductivity of LATP is reduced, and a large amount of energy is consumed. The hot-pressing sintering technology has higher sintering temperature and better heat preservation effect, and applies pressure in the sintering process to improve the compactness of the material, but also needs huge energy consumption. The spark plasma sintering is sintered in vacuum, has the characteristic of high temperature rise rate, and the prior sintered LATP ceramic sheet also obtains high ionic conductivity, but has higher cost and can not be produced in batch at present.
Reference to the literature
[1]A.Manthiram,X.Yu,and S.Wang,“Lithium battery chemistries enabled by solid-state electrolytes,”Nat.Rev.Mater.,vol.2,no.4,pp.1–16,2017,doi:10.1038/natrevmats.2016.103.
[2]R.DeWees and H.Wang,“Synthesis and Properties of NaSICON-type LATP and LAGP Solid Electrolytes,”ChemSusChem,vol.12,no.16,pp.3713–3725,2019,doi:10.1002/cssc.201900725.
[3]K.Arbi,W.Bucheli,R.Jiménez,and J.Sanz,“High lithium ion conducting solid electrolytes based on NASICON Li1+xAlxM2-x(PO4)3materials(M＝Ti,Ge and 0≤x≤0.5),”J.Eur.Ceram.Soc.,vol.35,no.5,pp.1477–1484,2015,doi:10.1016/j.jeurceramsoc.2014.11.023.
[4]M.Kotobuki,M.Koishi,and Y.Kato,“Preparation ofLi1.5Al0.5Ti1.5(PO4)3solid electrolyte via a co-precipitation method,”Ionics(Kiel).,vol.19,no.12,pp.1945–1948,2013,doi:10.1007/s11581-013-1000-4.
[5]P.Zhang,M.Matsui,Y.Takeda,O.Yamamoto,and N.Imanishi,“Water-stable lithium ion conducting solid electrolyte ofiron and aluminum doped NASICON-type LiTi2(PO4)3,”Solid State Ionics,vol.263,pp.27–32,2014,doi:10.1016/j.ssi.2014.04.017。
Disclosure of Invention
In order to overcome the above problems, the present invention provides a compact solid electrolyte LATP (Li)1.3Al0.3Ti1.7(PO4)3) The sintering method of (1).
The invention discloses a sintering method of a compact solid electrolyte LATP, which comprises the following steps:
step 1: 10g of LATP powder with the purity of more than 99 percent is taken and ball-milled for 12 hours by a planetary ball mill with the rotating speed of 300 rpm/min.
Step 2: 0.2g of LATP powder is taken out from the step 1, put into a round die and pressed into a uniform wafer with certain strength under the uniaxial pressure of 300 MPa.
And step 3: and (3) taking out the wafer in the step (2), putting the wafer between two graphite felts with the size of 80 x 30 x 3mm, introducing a certain current voltage to two ends of each graphite felt, ensuring a certain sintering time, and then cooling to room temperature to obtain a required compact ceramic sample, wherein the argon flow is 50-250 ml/min.
Further, the current voltage in the step 3 is 0-60V, and the direct current is 0-30A.
Furthermore, the sintering time in the step 3 is 0-120s, and the cooling mode is natural cooling to the room temperature.
The beneficial technical effects of the invention are as follows:
(1) the tablet press presses the LATP powder into uniform small round pieces, and the uniform small round pieces are placed between two graphite felts, and certain current and voltage are introduced into the graphite felts to start heating and maintain for a certain time. Only very short sintering times are required in this sintering process to obtain a dense LATP ceramic sheet with high ionic conductivity.
(2) Under the conditions of certain current and voltage and certain time, the wafer does not crack due to uneven temperature distribution, and abnormal coarseness of crystal grains due to long-time continuous high temperature is avoided; rapidly cooling after sintering is finished, the cooling rate does not need to be controlled, the thickness of the sintered LATP wafer is 0.7mm, the diameter of the sintered LATP wafer is 13mm, and the wafer does not crack; the lithium ion conductivity can be compared to LATP wafers sintered by conventional pressureless sintering techniques.
Drawings
FIG. 1 shows X-ray diffraction patterns before and after sintering.
FIG. 2 is the electrochemical impedance spectra of the sintered LATP samples of examples 1, 2, and 3.
Fig. 3 is an SEM image of the LATP ceramic sheet prepared in example 1.
Fig. 4 is an SEM image of the LATP ceramic sheet prepared in example 2.
Fig. 5 is an SEM image of the LATP ceramic sheet prepared in example 3.
Detailed Description
The invention is described in further detail below with reference to the figures and specific embodiments.
Example 1
Step 1: taking 10g of LATP powder with the purity of more than 99 percent, and ball-milling for 12 hours by a planetary ball mill at the rotating speed of 300 rpm/min;
step 2: taking out 0.2g of LATP powder from the step 1, putting the powder into a round die, and pressing the powder into a uniform ceramic wafer with certain strength under the uniaxial pressure of 300 MPa;
and step 3: taking out the wafer in the step 2, putting the wafer between two graphite felts with the size of 80 x 30 x 3mm, introducing constant current 20A at two ends of the graphite felts for 60s, and then cooling to room temperature to obtain the needed LATP ceramic wafer, wherein the argon flow is 200 ml/min;
according to the LATP ceramic chip obtained by the scheme, the graphite felt generates high temperature rapidly under the current, heat is conducted to a sample, the sample is rapidly sintered and compact, the sample has certain strength, the relative density is 80.9%, the sintered sample is complete, the sample is not oxidized by graphite, and the ionic conductivity is 1.66 multiplied by 10-4S cm-1。
Example 2
Step 1: taking 10g of LATP powder with the purity of more than 99 percent, and ball-milling for 12 hours by a planetary ball mill at the rotating speed of 300 rpm/min;
step 2: taking out 0.2g of LATP powder from the step 1, putting the powder into a round die, and pressing the powder into a uniform ceramic wafer with certain strength under the uniaxial pressure of 300 MPa;
and step 3: taking out the wafer in the step 2, putting the wafer between two graphite felts with the size of 80 x 30 x 3mm, introducing constant current 20A at two ends of the graphite felts for 80s, and then cooling to room temperature to obtain the needed LATP ceramic wafer, wherein the argon flow is 200 ml/min;
the LATP product obtained in this protocol was denser, with a relative density of 83.3% and an ionic conductivity of 2.34 x 10 relative to example 2-4S cm-1The sample was intact and the surface was not oxidized.
Example 3
Step 1: taking 10g of LATP powder with the purity of more than 99 percent, and ball-milling for 12 hours by a planetary ball mill at the rotating speed of 300 rpm/min;
step 2: taking out 0.2g of LATP powder from the step 1, putting the powder into a round die, and pressing the powder into a uniform ceramic wafer with certain strength under the uniaxial pressure of 300 MPa;
and step 3: and (3) taking out the wafer in the step (2), putting the wafer between two graphite felts with the size of 80 x 30 x 3mm, introducing constant current 20A to the two ends of the graphite felts for 100s, and then cooling to room temperature to obtain the needed LATP ceramic wafer, wherein the argon flow is 200 ml/min.
Compared with the examples 1, 2 and 3, the LATP ceramic sheet obtained by the scheme is the most compact, the relative density is 90 percent, and the ionic conductivity is 4.7 multiplied by 10-4S cm-1The performance is already equivalent to that of the traditional sintering.
According to the invention, a sintering method for compacting ceramic based on ultra-high temperature sintering is utilized, a certain current and voltage are introduced into the graphite felt, the LATP ceramic sheet is rapidly sintered under the condition of extremely high temperature rising rate, and the ceramic sheet is naturally cooled after being kept for a certain time. FIG. 1 is an X-ray diffraction pattern before and after sintering, and FIG. 2 is an electrochemical impedance spectrum of a sample of LATP sintered in examples 1, 2, and 3. LATP is free of by-products and is not oxidized by graphite after sintering in this process. The ion conductivity of the LATP ceramic sheet obtained in the embodiment 3 is highest, and the performance of traditional sintering is achieved, however, the traditional sintering needs heat preservation for 6-12 hours, the temperature rising and heat preservation time of the method only needs 100s, the sintered LATP ceramic sheet has certain mechanical strength, the surface is smooth and flat, no crack exists, and the LATP ceramic sheet can be directly used for battery assembly. The SEM images of fig. 3, 4 and 5 show that as the heating time increases, grains start to grow, grain gaps start to shrink, pores become less, the relative density also increases, and the ion conductivity also increases. The method is simple to operate, and can meet the requirements on equipment for generating direct current, wherein the current is 0-30A, and the voltage is in the range of 0-60V. The sintering time is far shorter than that of the existing sintering method, and the method is also suitable for other ceramic solid electrolytes.

Claims (3)

1. A sintering method of a compact solid electrolyte LATP is characterized by comprising the following steps:
step 1: taking 10g of LATP powder with the purity of more than 99 percent, and ball-milling for 12 hours by a planetary ball mill at the rotating speed of 300 rpm/min;
step 2: taking out 0.2g of LATP powder from the step 1, putting the powder into a circular die, and pressing the powder into a uniform wafer under the uniaxial pressure of 300 MPa;
and step 3: and (3) taking out the wafer in the step (2), putting the wafer between two graphite felts with the size of 80 x 30 x 3mm, introducing current voltage to two ends of the graphite felts, cooling to room temperature after sintering to obtain a required compact ceramic sample, wherein the flow of argon is 50-250 ml/min.
2. The sintering method of compact solid electrolyte LATP as claimed in claim 1, wherein the current voltage in step 3 is 0-60V, 0-30A dc.
3. The method of claim 1 wherein said sintering time in step 3 is 0-120s and the cooling is natural cooling to room temperature.
CN202110816580.1A 2021-07-20 2021-07-20 Sintering method of compact solid electrolyte LATP Pending CN113429199A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130084504A1 (en) * 2011-09-30 2013-04-04 Michael Edward Badding Micromachined electrolyte sheet
WO2014003591A1 (en) * 2012-06-29 2014-01-03 Lneg - Laboratório Nacional De Energia E Geologia Process for manufacturing a solid oxide fuel cell electrolyte using microwave sintering
CN103496740A (en) * 2013-09-18 2014-01-08 武汉理工大学 Electric field activated sintering method of solid electrolyte material
CN110492170A (en) * 2019-08-30 2019-11-22 电子科技大学 A kind of high ionic conductivity composite solid electrolyte and preparation method thereof
CN111916822A (en) * 2020-08-27 2020-11-10 电子科技大学 Co-sintering modified solid electrolyte ceramic chip and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130084504A1 (en) * 2011-09-30 2013-04-04 Michael Edward Badding Micromachined electrolyte sheet
WO2014003591A1 (en) * 2012-06-29 2014-01-03 Lneg - Laboratório Nacional De Energia E Geologia Process for manufacturing a solid oxide fuel cell electrolyte using microwave sintering
CN103496740A (en) * 2013-09-18 2014-01-08 武汉理工大学 Electric field activated sintering method of solid electrolyte material
CN110492170A (en) * 2019-08-30 2019-11-22 电子科技大学 A kind of high ionic conductivity composite solid electrolyte and preparation method thereof
CN111916822A (en) * 2020-08-27 2020-11-10 电子科技大学 Co-sintering modified solid electrolyte ceramic chip and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YONG LIN ET AL.: "Ultrafast high-temperature sintering (UHS) of Li1.3Al0.3Ti1.7(PO4)3", 《CERAMICS INTERNATIONAL》 *

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Application publication date: 20210924