CN111848151A - Titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof - Google Patents

Titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof Download PDF

Info

Publication number
CN111848151A
CN111848151A CN202010797301.7A CN202010797301A CN111848151A CN 111848151 A CN111848151 A CN 111848151A CN 202010797301 A CN202010797301 A CN 202010797301A CN 111848151 A CN111848151 A CN 111848151A
Authority
CN
China
Prior art keywords
phase
ball milling
absorbing material
lamtp
phase ceramic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010797301.7A
Other languages
Chinese (zh)
Other versions
CN111848151B (en
Inventor
陈丹
周影影
唐健江
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Aeronautical University
Original Assignee
Xian Aeronautical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Aeronautical University filed Critical Xian Aeronautical University
Priority to CN202010797301.7A priority Critical patent/CN111848151B/en
Publication of CN111848151A publication Critical patent/CN111848151A/en
Application granted granted Critical
Publication of CN111848151B publication Critical patent/CN111848151B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • C04B35/62222—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic coatings
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/442—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/666—Applying a current during sintering, e.g. plasma sintering [SPS], electrical resistance heating or pulse electric current sintering [PECS]
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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 titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material and a preparation method and application thereof, wherein the preparation method comprises the following steps: the raw material is Li2CO3、NH4H2PO4、TiO2、Al2O3MgO, the ratio of the amounts of the substances being 1.1(0.65+0.5 x): 3: 1.7: 0.15-0.5 x: x and x are 0.01-0.1; after mixing, the raw materials are presintered at 880-920 ℃, and then plasma discharge sintering is carried out at 980-1020 ℃. The invention directly prepares the LAMTP single-phase ceramic wave-absorbing material with obvious wave-absorbing performance without adopting composite materials, and avoids the existence of the composite materials in long-term useOxidation and interfacial reaction problems.

Description

Titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of wave-absorbing material preparation, and relates to a titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material, and a preparation method and application thereof.
Background
With the further development of military science and technology, the modern information war is hidden from the weaponThe body performance puts the use demands at high temperature. The common high-temperature wave-absorbing material is usually compounded by adopting an absorbent and a substrate, wherein the substrate is usually made of high-temperature-resistant ceramic or glass, and the absorbent is usually a high-conductivity carbon material, such as SiC, ZnO and Ti3SiC2And the electromagnetic parameters are regulated and controlled by adjusting the type, content, size, morphology and distribution state of the absorbent. However, the composite material has problems of oxidation and interfacial reaction when used for a long time.
Li1.3Al0.3Ti1.7(PO4)3From TiO6Hexahedron and PO4Skeleton structure composed of tetrahedrons, Al3+The ions may be located on tetrahedra or hexahedron, Li+The ions shuttle in gaps of hexahedron and tetrahedron, and the ion conduction is high, so that the ion conduction type energy storage device is widely applied to the field of energy storage. With Li1.3Al0.3Ti1.7(PO4)3The single-phase ceramic is used as a wave-absorbing material, the dielectric constant has a frequency dispersion effect, the absorption bandwidth can be effectively expanded, the loss mechanism is electric conduction loss, electromagnetic parameters can be regulated and controlled by adjusting the electric conductivity, the wave-absorbing performance is optimized, and the problems of interface reaction and diffusion existing in long-term use of the low-electric-conductivity ceramic matrix/high-electric-conductivity absorbent composite material can be solved. Currently, Li prepared by solid phase method1.3Al0.3Ti1.7(PO4)3The single-phase ceramic has a conductivity of 1 × 10-4S·cm-3～4×10-4S·cm-3The conductivity of the material is yet to be improved; li1.3Al0.3Ti1.7(PO4)3The real part of the dielectric constant of the single-phase ceramic is 10.2-13.1, and the imaginary part of the single-phase ceramic is 2.2-3.3; in the X wave band, the absorption bandwidth with the reflectivity lower than-10 dB is 2.25GHz, the absorption bandwidth is still to be expanded, the lowest reflectivity is-13.4 dB, and the absorption peak is still to be deepened.
Therefore, in order to solve the above problems, it is necessary to use Li1.3Al0.3Ti1.7(PO4)3The single-phase ceramic is modified to improve the conductivity, increase the absorption bandwidth and deepen the absorption peak so as to improve the wave absorption of the single-phase ceramicPerformance, and the application range is enlarged.
Disclosure of Invention
In order to achieve the aim, the invention provides a titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material, a preparation method and application thereof, which solve the problem of Li existing in the prior art1.3Al0.3Ti1.7(PO4)3The wave-absorbing performance of the single-phase ceramic needs to be improved.
Wherein the lithium magnesium aluminum titanium phosphate is Li1.3+xAl0.3-xMgxTi1.7(PO4)3The Chinese name of (2); LAMTP is Li1.3+ xAl0.3-xMgxTi1.7(PO4)3The English language of (1) is abbreviated.
The technical scheme adopted by the invention is that the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material has a chemical formula general formula of Li1.3+xAl0.3-xMgxTi1.7(PO4)3And x is 0.01-0.1.
Further, Li1.3+xAl0.3-xMgxTi1.7(PO4)3Has a conductivity of 2X 10-3S·cm-3～5×10-3S·cm-3(ii) a The Li1.3+xAl0.3-xMgxTi1.7(PO4)3The real part range of the dielectric constant is 11.3-14.2, and the imaginary part range is 3.0-4.0.
The invention also aims to provide a preparation method of the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material, which comprises the following steps:
s10, preparing raw materials: in terms of the ratio of the amounts of substances 1.1 × (0.65+0.5 ×): 3: 1.7: (0.15-0.5 x): weighing Li in proportion of x2CO3、NH4H2PO4、TiO2、Al2O3MgO; wherein x is 0.01-0.1; the purity of each raw material is more than 99.99 percent; in order to compensate for the high-temperature volatilization of Li element, Li in the raw material2CO3In the amount of (b) to be added in a stoichiometric ratioThe mass is increased by 10 wt%;
s20, primary ball milling and drying: mixing the prepared raw materials of S1, and then carrying out primary ball milling and drying treatment to obtain precursor powder; the purpose of ball milling in the step S20 is to uniformly mix the raw materials and prepare for the high-temperature solid-phase reaction of the presintering step S30;
s30, pre-burning: placing the precursor powder obtained in the step S20 into a crucible, transferring the crucible into an air furnace, heating to 880-920 ℃ at the heating rate of 5 ℃/min, preserving the heat for 4-8 h, cooling along with the furnace, and grinding the obtained product to obtain single-phase Li1.3+ xAl0.3-xMgxTi1.7(PO4)3Coarsely grinding the particles; wherein, the crucible is preferably a corundum crucible;
among them, in S30, the purpose of the pre-firing is to synthesize single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3(ii) a The pre-firing temperature and time are based on Li2CO3、NH4H2PO4、TiO2、Al2O3Reaction to form Li1.3Al0.3Ti1.7(PO4)3The DSC curve of (1) shows that if the temperature is below 880 ℃ or above 920 ℃ and the heat preservation time is below 4h or above 8h, Li cannot be synthesized1.3Al0.3Ti1.7(PO4)3Or impurities appear, and Mg can not enter the Al position.
S30 obtaining single-phase Li of pre-sintered product1.3+xAl0.3-xMgxTi1.7(PO4)3Can not be directly used as a wave-absorbing material because the wave-absorbing material can be used only by having higher density, if the precursor powder obtained by S20 is molded directly and then presintered by S30 to obtain a molded body or is directly used as a coating material, a large amount of air exists among particles of the molded body or the coating, the dielectric constant and the electric conduction loss of the molded body or the coating can be reduced, and the wave-absorbing performance of the molded body or the coating is influenced, so that the wave-absorbing material can be used for single-phase Li obtained by S301.3+ xAl0.3-xMgxTi1.7(PO4)3Densification treatment is carried out to obtain the product with good wave-absorbing performanceThe material of (a);
s40, secondary ball milling and drying: the single-phase Li obtained in S301.3+xAl0.3-xMgxTi1.7(PO4)3Carrying out secondary ball milling and drying treatment on the coarse ground particles to obtain single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Finely grinding the particles;
s50, sintering: the single-phase Li obtained in S401.3+xAl0.3-xMgxTi1.7(PO4)3Placing the finely ground particles into a graphite mould, transferring the graphite mould into a plasma discharge sintering furnace, heating to 980-1020 ℃ at a heating rate of 80-120 ℃/min under the pressure condition of 20-40 MPa, preserving the heat for 4-8 min, and then cooling along with the furnace to obtain the material with the chemical formula of Li1.3+xAl0.3-xMgxTi1.7(PO4)3The single-phase ceramic wave-absorbing material of LAMTP is prepared from magnesium aluminum lithium titanium phosphate.
Wherein, in S50, single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3The purpose of placing the fine ground particles into a graphite mould for plasma discharge sintering is as follows: by using the principle of sintering under pressure while discharging plasma, dense Li is obtained1.3+xAl0.3- xMgxTi1.7(PO4)3Single-phase ceramic wave-absorbing material.
The shrinkage rate is calculated according to the volume difference of the samples before and after sintering, the sintering temperature is lower than 980 ℃, the samples are not compact, the sintering temperature is higher than 1020 ℃, the samples are over-sintered, and the shrinkage rate difference of the samples is large along with the change of the sintering temperature; when the sintering temperature is 980-1020 ℃, the shrinkage rate of the sample is unchanged along with the change of the sintering temperature, so that the sintering temperature is selected to be 980-1020 ℃. Because of different contents of doped Mg, the sintering temperature is within a range, and the sintering temperatures are slightly different for different contents.
Further, in S10, x is 0.04.
Further, in S20, the primary ball milling and drying specifically includes the following steps:
s21, primary ball milling: mixing the prepared raw materials of S10, pouring the mixture into a ball milling tank, adding grinding balls, wherein the mass ratio of the ball materials is 20:1, adding absolute ethyl alcohol to submerge the grinding balls and the mixed raw materials to 2/3 of the ball milling tank, and carrying out ball milling treatment for 8 hours at the speed of 250rad/min to obtain precursor slurry;
s22, primary drying: and after the primary ball milling is finished, pouring out the precursor slurry in the ball milling tank, putting the precursor slurry into an oven at 80 ℃ for primary drying after the absolute ethyl alcohol in the precursor slurry is completely volatilized to obtain a precursor material, grinding the precursor material, and sieving by using a 200-mesh sieve to obtain precursor powder. Wherein, the specific process of primary drying is as follows: pouring the precursor slurry in the ball milling tank into a clean stainless steel plate, then putting the plate into a fume hood, after the absolute ethyl alcohol of the precursor slurry is completely volatilized and becomes viscous, putting the plate into an oven at 80 ℃, and taking out the plate after the material is cracked and has no wet trace to obtain a precursor material;
further, in S30, the pre-firing specifically includes: placing the precursor powder obtained in S20 into a crucible, transferring into an air furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 6h, cooling along with the furnace, and grinding the obtained product to obtain single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3And (4) coarsely grinding the particles.
Further, in S40, performing secondary ball milling and drying, specifically:
s41, secondary ball milling: the single-phase Li obtained in S301.3+xAl0.3-xMgxTi1.7(PO4)3Pouring the coarse ground particles into a ball milling tank, adding grinding balls with a ball-material ratio of 30:1, and adding absolute ethyl alcohol to submerge the grinding balls and the single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Coarsely grinding the particles to 2/3 position of a ball milling tank, and performing secondary ball milling at 300rad/min for 8h to obtain single-phase Li1.3+ xAl0.3-xMgxTi1.7(PO4)3Sizing agent; wherein, the purpose of secondary ball milling of S41 is to reduce synthesized single-phase Li1.3+xAl0.3- xMgxTi1.7(PO4)3The size of the coarse ground particles;
s42, secondary drying: after the secondary ball milling is finished, the single-phase Li in the ball milling tank is used1.3+xAl0.3-xMgxTi1.7(PO4)3Pouring out the slurry until single-phase Li is obtained1.3+xAl0.3-xMgxTi1.7(PO4)3After the absolute ethyl alcohol in the slurry is completely volatilized, the slurry is placed into an oven at 80 ℃ for secondary drying to obtain single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Material preparation; mixing single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Grinding the materials, and sieving with a 200-mesh sieve to obtain single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Finely grinding the particles. Wherein, the specific process of secondary drying is as follows: mixing single-phase Li in a ball milling tank1.3+xAl0.3-xMgxTi1.7(PO4)3Pouring the slurry into a clean stainless steel plate, placing the plate into a fume hood, and waiting for single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3After the absolute ethyl alcohol of the slurry is volatilized and becomes viscous, the slurry is placed into an oven at 80 ℃, and the slurry is taken out after the materials are cracked and have no any wetting trace, so that the single-phase Li is obtained1.3+ xAl0.3-xMgxTi1.7(PO4)3And (3) feeding.
In S21 and S41, the ball milling tank is made of any one of stainless steel, nylon, polytetrafluoroethylene, alumina and zirconia; the grinding ball is made of any one of stainless steel, aluminum oxide and zirconium oxide.
Further, in S50, the sintering process specifically includes: the single-phase Li obtained in S401.3+xAl0.3-xMgxTi1.7(PO4)3Placing the fine ground particles into a graphite mold, transferring into a plasma discharge sintering furnace, heating to 1000 deg.C at a temperature rise rate of 100 deg.C/min under a pressure of 30MPa, and maintainingHeating for 5min, and furnace cooling to obtain Li1.3+xAl0.3-xMgxTi1.7(PO4)3Single-phase ceramic wave-absorbing material.
Further, single-phase Li obtained in S401.3+xAl0.3-xMgxTi1.7(PO4)3The finely ground particles can also be used as raw materials of stealth coatings to carry out supersonic plasma spraying on the surfaces of objects needing stealth to obtain Li1.3+xAl0.3-xMgxTi1.7(PO4)3A single phase ceramic coating.
The invention also aims to provide application of the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material in the field of wave-absorbing materials.
The invention has the beneficial effects that:
(1) the invention utilizes low-valence element Mg to dope Li1.3Al0.3Ti1.7(PO4)3So that the doping elements partially replace Al sites and reduce the Li content of the framework ion pairs+The binding force of ions optimizes Li+The channel size of ion migration increases the carrier Li+The quantity of the ions effectively improves the conductivity and the dielectric constant of the composite material, adjusts the frequency dispersion effect of the composite material and improves the wave absorbing performance of the composite material.
(2) Li prepared by the invention1.3+xAl0.3-xMgxTi1.7(PO4)3The single-phase ceramic wave-absorbing material has the conductivity of (2-5) x 10-3S·cm-3In comparison with Li1.3Al0.3Ti1.7(PO4)3The conductivity of the conductive material is improved by one order of magnitude; the real part of the dielectric constant is 11.3-14.2, the imaginary part is 3.0-4.0, and the real part is more Li than Li1.3Al0.3Ti1.7(PO4)3The dielectric property of the dielectric ceramic is obviously improved; in the X wave band, the absorption bandwidth with the reflectivity lower than-10 dB is 2.98GHz, and the absorption bandwidth is more Li1.3Al0.3Ti1.7(PO4)3Has obvious improvement, the lowest reflectivity is-17.2 dB, and the absorption peak is more Li1.3Al0.3Ti1.7(PO4)3There is a significant deepening.
(3) Li prepared by the invention1.3+xAl0.3-xMgxTi1.7(PO4)3(x is more than or equal to 0.01 and less than or equal to 0.1) the dielectric constant of the single-phase ceramic has a frequency dispersion effect, which is beneficial to the expansion of absorption bandwidth, and the polarization mechanism is thermionic relaxation polarization, Li+The activation energy of ion migration determines the polarization capability, the loss mechanism is the conductance loss, and the conductivity determines the loss value.
(4) The invention directly prepares Li without adopting composite material1.3+xAl0.3-xMgxTi1.7(PO4)3The single-phase ceramic wave-absorbing material avoids the problems of oxidation and interface reaction existing in the long-term use of the composite material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows Li obtained in example 3 of the present invention1.34Al0.26Mg0.04Ti1.7(PO4)3XRD pattern of single-phase ceramic wave-absorbing material.
FIG. 2 shows Li obtained in example 3 of the present invention1.34Al0.26Mg0.04Ti1.7(PO4)3SEM image of single-phase ceramic wave-absorbing material.
FIG. 3 is Li obtained in comparative example 1 of the present invention1.3Al0.3Ti1.7(PO4)3Single-phase ceramic material and Li prepared in example 31.34Al0.26Mg0.04Ti1.7(PO4)3The dielectric constant curve diagram of the single-phase ceramic wave-absorbing material.
FIG. 4 shows Li obtained in example 3 of the present invention1.34Al0.26Mg0.04Ti1.7(PO4)3Reflectivity curve diagrams of the single-phase ceramic wave-absorbing material under different thicknesses.
FIG. 5 is Li obtained in comparative example 11.3Al0.3Ti1.7(PO4)3Single-phase ceramic material and Li prepared in example 31.34Al0.26Mg0.04Ti1.7(PO4)3Reflectivity curve diagrams of the single-phase ceramic wave-absorbing material under respective optimal thicknesses.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Li1.31Al0.29Mg0.01Ti1.7(PO4)3The preparation method of the single-phase ceramic wave-absorbing material comprises the following steps:
(1) preparing raw materials: according to the ratio of the amount of the materials 0.7205: 3: 1.7: 0.145: li was weighed in a proportion of 0.012CO3、NH4H2PO4、TiO2、Al2O3MgO; wherein the purity of each raw material is more than 99.99 percent;
(2) and ball milling for the first time: mixing the prepared raw materials in the step (1), pouring the mixture into a polytetrafluoroethylene ball milling tank, adding zirconia grinding balls, wherein the mass ratio of the balls to the materials is 20:1, adding absolute ethyl alcohol to submerge the grinding balls and the mixed raw materials to 2/3 of the ball milling tank, and performing primary ball milling treatment for 8 hours at the speed of 250rad/min to obtain precursor slurry;
(3) primary drying: after primary ball milling is finished, pouring the precursor slurry in the ball milling tank into a clean stainless steel plate, then putting the stainless steel plate into a fume hood, after absolute ethyl alcohol of the precursor slurry is completely volatilized and becomes viscous, putting the precursor slurry into an oven at 80 ℃, taking the precursor slurry out after the material is cracked and has no any wet trace (completely dried), obtaining a precursor material, manually grinding the precursor material by adopting an agate mortar until the precursor material is completely dispersed, and sieving the precursor material by using a 200-mesh sieve to obtain precursor powder;
(4) pre-burning: placing the precursor powder obtained in the step (3) into a corundum crucible, transferring the corundum crucible into an air furnace, heating to 880 ℃ at the heating rate of 5 ℃/min, preserving heat for 4 hours, cooling along with the furnace, manually grinding the obtained product by adopting an agate mortar to completely disperse the product, and obtaining single-phase Li1.31Al0.29Mg0.01Ti1.7(PO4)3Coarsely grinding the particles;
(5) and (3) secondary ball milling: the single-phase Li obtained in the step (4)1.31Al0.29Mg0.01Ti1.7(PO4)3Pouring the coarse ground particles into a polytetrafluoroethylene ball mill tank, adding zirconia grinding balls with the ball-material ratio of 30:1, and adding absolute ethyl alcohol to submerge the grinding balls and the single-phase Li1.31Al0.29Mg0.01Ti1.7(PO4)3Coarsely grinding the particles to 2/3 position of a ball milling tank, and performing secondary ball milling at 300rad/min for 8h to obtain single-phase Li1.31Al0.29Mg0.01Ti1.7(PO4)3Sizing agent;
(6) and (3) secondary drying: after the secondary ball milling is finished, the single-phase Li in the ball milling tank is used1.31Al0.29Mg0.01Ti1.7(PO4)3Pouring the slurry into a clean stainless steel plate, placing the plate into a fume hood, and waiting for single-phase Li1.31Al0.29Mg0.01Ti1.7(PO4)3After the absolute ethyl alcohol of the slurry is volatilized and becomes viscous, the slurry is placed into an oven at 80 ℃, and the slurry is taken out after the material is cracked and has no any wetting trace (is completely dried), so that the single-phase Li is obtained1.31Al0.29Mg0.01Ti1.7(PO4)3Material preparation; mixing single-phase Li1.31Al0.29Mg0.01Ti1.7(PO4)3The materials are manually ground by an agate mortar and sieved by a 200-mesh sieve to obtain the productTo single phase Li1.31Al0.29Mg0.01Ti1.7(PO4)3Finely grinding the particles;
(7) and (3) sintering: the single-phase Li obtained in S401.31Al0.29Mg0.01Ti1.7(PO4)3Placing the finely ground particles into a graphite mold, transferring the graphite mold into a plasma discharge sintering furnace, heating to 980 ℃ at a heating rate of 80 ℃/min under the pressure condition of 20MPa, preserving the heat for 4min, and cooling along with the furnace to obtain Li1.31Al0.29Mg0.01Ti1.7(PO4)3Single-phase ceramic wave-absorbing material.
Li obtained in example 11.31Al0.29Mg0.01Ti1.7(PO4)3The single-phase ceramic wave-absorbing material has the conductivity of 2 multiplied by 10- 3S·cm-3。
Example 2
Li1.4Al0.2Mg0.1Ti1.7(PO4)3The preparation method of the single-phase ceramic wave-absorbing material comprises the following steps:
the ratio in terms of the amount of substances in the division (1) is 0.77: 3: 1.7: 0.1: li was weighed in a proportion of 0.12CO3、NH4H2PO4、TiO2、Al2O3、MgO；
(3) Heating to 920 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 8 hours;
(7) heating to 1020 ℃ at the heating rate of 120 ℃/min under the pressure condition of 40MPa, and keeping the temperature for 8 min.
The remaining steps were the same as in example 1.
Li obtained in example 21.4Al0.2Mg0.1Ti1.7(PO4)3The single-phase ceramic wave-absorbing material has the conductivity of 4 multiplied by 10- 3S·cm-3。
Example 3
Li1.34Al0.26Mg0.04Ti1.7(PO4)3The preparation method of the single-phase ceramic wave-absorbing material comprises the following steps:
the ratio in terms of the amount of substances in the division (1) is 0.737: 3: 1.7: 0.13: li was weighed in a proportion of 0.042CO3、NH4H2PO4、TiO2、Al2O3、MgO；
(3) Heating to 900 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 6 hours;
(7) heating to 1000 ℃ at a heating rate of 100 ℃/min under the pressure condition of 30MPa, and preserving heat for 5 min.
The remaining steps were the same as in example 1.
Li obtained in example 31.34Al0.26Mg0.04Ti1.7(PO4)3The single-phase ceramic wave-absorbing material has the conductivity of 5 multiplied by 10- 3S·cm-3。
Example 4
Li1.37Al0.23Mg0.07Ti1.7(PO4)3The preparation method of the single-phase ceramic wave-absorbing material comprises the following steps:
the ratio in terms of the amount of substances in the division (1) is 0.754: 3: 1.7: 0.115: li was weighed in a proportion of 0.072CO3、NH4H2PO4、TiO2、Al2O3、MgO；
The remaining steps were the same as in example 3.
Li obtained in example 41.34Al0.26Mg0.04Ti1.7(PO4)3The single-phase ceramic wave-absorbing material has the conductivity of 4.5 multiplied by 10-3S·cm-3。
Comparative example 1
Li1.3Al0.3Ti1.7(PO4)3The preparation method of the single-phase ceramic material comprises the following steps:
the ratio in terms of the amount of substances in the division (1) is 0.65: 3: 1.7: li was weighed in a proportion of 0.152CO3、NH4H2PO4、TiO2、Al2O3；
The remaining steps were the same as in example 3.
Li obtained in comparative example 11.3Al0.3Ti1.7(PO4)3Conductivity 2X 10 of single-phase ceramic material-4S·cm-3。
Experimental example 1
For Li prepared in example 31.34Al0.26Mg0.04Ti1.7(PO4)3XRD test is carried out on the single-phase ceramic wave-absorbing material, and the test result is shown in figure 1. As shown in FIG. 1, the crystalline phase of the wave-absorbing material prepared in example 1 of the present invention is Li1.3Al0.3Ti1.7(PO4)3Although the single phase was observed from the enlarged view of diffraction peaks at the 24 DEG to 25 DEG positions, the diffraction peak at this position was at a position closer to Li1.3Al0.3Ti1.7(PO4)3The diffraction peak at the position is shifted towards a small angle in pure phase, which indicates that the wave-absorbing material prepared in the embodiment has the doped product magnesium, and the diffraction peak is shifted towards a small angle according to a Bragg equation 2dsin theta-n lambda, wherein d is the interplanar spacing, theta is the diffraction angle, lambda is the wavelength, n is the reflection order, and the decrease of the diffraction angle indicates the increase of the interplanar spacing, thereby further proving that the ionic radius is larger than that of Al3+
Figure BDA0002626136050000081
Ionic Mg2+
Figure BDA0002626136050000082
Successful ion doping into Li1.3Al0.3Ti1.7(PO4)3Formation of Li1.34Al0.26Mg0.04Ti1.7(PO4)3Single-phase ceramic wave-absorbing material. Wherein the dotted line position in the enlarged view of diffraction peaks at positions 24 to 25 ℃ in FIG. 1 represents undoped Li1.3Al0.3Ti1.7(PO4)3The diffraction peak of (1).
Experimental example 2
For Li prepared in example 31.34Al0.26Mg0.04Ti1.7(PO4)3SEM test is carried out on the microscopic morphology of the single-phase ceramic wave-absorbing material, and the test result is shown in figure 2. As can be seen from FIG. 2, Li obtained in example 31.34Al0.26Mg0.04Ti1.7(PO4)3The grain size of the single-phase ceramic wave-absorbing material is between 1 mu m and 18 mu m, and the density is more than 95 percent.
Experimental example 3
For Li prepared in example 31.34Al0.26Mg0.04Ti1.7(PO4)3The wave-absorbing performance of the single-phase ceramic wave-absorbing material is tested, and the test results are shown in figures 3-5.
First, Li obtained in example 31.34Al0.26Mg0.04Ti1.7(PO4)3Single-phase ceramic wave-absorbing material and Li prepared in comparative example 11.3Al0.3Ti1.7(PO4)3The dielectric constant of the single-phase ceramic material was tested and the dielectric constant curve is shown in fig. 3. As can be seen from FIG. 3, Li obtained in example 31.34Al0.26Mg0.04Ti1.7(PO4)3Single-phase ceramic wave-absorbing material and Li prepared in comparative example 11.3Al0.3Ti1.7(PO4)3The dielectric constant of the single-phase ceramic material shows a frequency dispersion effect along with the change of frequency. Li obtained in comparative example 11.3Al0.3Ti1.7(PO4)3The real part of the dielectric constant of the single-phase ceramic material is 10.2-13.1, and the imaginary part is 2.2-3.3. Li obtained in example 31.34Al0.26Mg0.04Ti1.7(PO4)3The real part of the dielectric constant of the single-phase ceramic wave-absorbing material is 11.3-14.2, and the imaginary part of the single-phase ceramic wave-absorbing material is 3.0-4.0, which are both increased compared with the comparative example 1.
Next, for Li obtained in example 31.34Al0.26Mg0.04Ti1.7(PO4)3Single-phase ceramic wave-absorbing materialThe reflectance curve at the same thickness was tested, and the test results are shown in fig. 4. As can be seen from fig. 4, the absorption peak shifts to a low frequency as the thickness increases. By selecting the thickness having the widest absorption bandwidth as the optimum thickness at the thinnest possible thickness, Li obtained in example 31.34Al0.26Mg0.04Ti1.7(PO4)3The optimal thickness of the single-phase ceramic wave-absorbing material is 2.1 mm.
Finally, Li obtained in example 31.34Al0.26Mg0.04Ti1.7(PO4)3Single-phase ceramic wave-absorbing material and Li prepared in comparative example 11.3Al0.3Ti1.7(PO4)3The reflectivity curves of the single-phase ceramic materials at the respective optimum thicknesses were tested, and the test results are shown in fig. 5. As can be seen from FIG. 5, Li obtained in comparative example 11.3Al0.3Ti1.7(PO4)3The optimal thickness of the single-phase ceramic material is 2.2mm, the bandwidth with the reflectivity lower than-10 dB in an X wave band is 2.25GHz, and the minimum reflectivity is-13.4 dB. Li obtained in example 3 in comparison with comparative example 11.34Al0.26Mg0.04Ti1.7(PO4)3The optimal thickness of the single-phase ceramic wave-absorbing material is 2.1mm, the optimal thickness is reduced compared with that of a comparative example 1, the bandwidth with the reflectivity lower than-10 dB in an X wave band is 2.98GHz, the bandwidth is obviously increased compared with that of the comparative example 1, the minimum reflectivity is-17.2 dB, and the absorption peak is deeper. This is due to the Li prepared in example 31.34Al0.26Mg0.04Ti1.7(PO4)3Proper amount of Mg is doped into single-phase ceramic wave-absorbing material2+After ionization, Li with proper size is obtained+The ion migration channel reduces the migration activation energy and obviously improves Li1.3Al0.3Ti1.7(PO4)3The conductivity of the ceramic increases the conductivity loss and obtains better wave-absorbing performance.
It is noted that, in the present application, relational terms such as first, second, third, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on the differences from the other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. A LAMTP single-phase ceramic wave-absorbing material of magnesium aluminum lithium titanium phosphate is characterized in that the general formula of the chemical formula is Li1.3+xAl0.3- xMgxTi1.7(PO4)3And the value of x is 0.01-0.1.
2. The LAMTP single-phase ceramic wave-absorbing material of claim 1, wherein Li is selected from the group consisting of Li, Mg, Al, Li, and Li1.3+xAl0.3-xMgxTi1.7(PO4)3Has a conductivity of 2X 10-3S·cm-3～5×10-3S·cm-3(ii) a The Li1.3+ xAl0.3-xMgxTi1.7(PO4)3The real part range of the dielectric constant is 11.3-14.2, and the imaginary part range is 3.0-4.0.
3. The preparation method of the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material according to claim 1 or 2, which is characterized by comprising the following steps:
s10, preparing raw materials: in terms of the ratio of the amounts of substances 1.1 × (0.65+0.5 ×): 3: 1.7: (0.15-0.5 x): weighing Li in proportion of x2CO3、NH4H2PO4、TiO2、Al2O3MgO; wherein the value of x is 0.01-0.1;
s20, primary ball milling and drying: mixing the prepared raw materials of S10, and then carrying out primary ball milling and drying treatment to obtain precursor powder;
s30, pre-burning: placing the precursor powder obtained in the step S20 into a crucible, transferring the crucible into an air furnace, heating to 880-920 ℃ at the heating rate of 5 ℃/min, preserving the heat for 4-8 h, cooling along with the furnace, and grinding the obtained product to obtain single-phase Li1.3+xAl0.3- xMgxTi1.7(PO4)3Coarsely grinding the particles;
s40, secondary ball milling and drying: the single-phase Li obtained in S301.3+xAl0.3-xMgxTi1.7(PO4)3Carrying out secondary ball milling and drying treatment on the coarse ground particles to obtain single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Finely grinding the particles;
s50, sintering: the single-phase Li obtained in S401.3+xAl0.3-xMgxTi1.7(PO4)3Placing the finely ground particles into a graphite mould, transferring the graphite mould into a plasma discharge sintering furnace, heating to 980-1020 ℃ at a heating rate of 80-120 ℃/min under the pressure condition of 20-40 MPa, preserving the heat for 4-8 min, and then cooling along with the furnace to obtain the material with the chemical formula of Li1.3+xAl0.3- xMgxTi1.7(PO4)3The single-phase ceramic wave-absorbing material of LAMTP is prepared from magnesium aluminum lithium titanium phosphate.
4. The method for preparing a LAMTP single-phase ceramic wave-absorbing material of magnesium aluminum lithium titanium phosphate according to claim 3, wherein in S10, the value of x is 0.04.
5. The preparation method of the LAMTP single-phase ceramic wave-absorbing material of claim 3, wherein in S20, the primary ball milling and drying specifically comprises the following steps:
s21, primary ball milling: mixing the prepared raw materials of S10, pouring the mixture into a ball milling tank, adding grinding balls, wherein the mass ratio of the ball materials is 20:1, adding absolute ethyl alcohol to submerge the grinding balls and the mixed raw materials to 2/3 of the ball milling tank, and carrying out ball milling treatment for 8 hours at the speed of 250rad/min to obtain precursor slurry;
s22, primary drying: and after the primary ball milling is finished, pouring out the precursor slurry in the ball milling tank, putting the precursor slurry into an oven at 80 ℃ for primary drying after the absolute ethyl alcohol in the precursor slurry is completely volatilized to obtain a precursor material, grinding the precursor material, and sieving by using a 200-mesh sieve to obtain precursor powder.
6. The preparation method of the LAMTP single-phase ceramic wave-absorbing material of claim 3, wherein in S30, the pre-sintering specifically comprises the following steps: placing the precursor powder obtained in S20 into a crucible, transferring into an air furnace, heating to 900 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 6h, cooling along with the furnace, and grinding the obtained product to obtain single-phase Li1.3+ xAl0.3-xMgxTi1.7(PO4)3And (4) coarsely grinding the particles.
7. The preparation method of the LAMTP single-phase ceramic wave-absorbing material of claim 3, wherein in S40, the secondary ball milling and drying specifically comprise:
s41, secondary ball milling: the single-phase Li obtained in S301.3+xAl0.3-xMgxTi1.7(PO4)3Pouring the coarse ground particles into a ball milling tank, adding grinding balls with the ball-material ratio of 30:1, and adding absolute ethyl alcohol to submerge the millSpheres and single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Coarsely grinding the particles to 2/3 position of a ball milling tank, and performing secondary ball milling at 300rad/min for 8h to obtain single-phase Li1.3+xAl0.3- xMgxTi1.7(PO4)3Sizing agent;
s42, secondary drying: after the secondary ball milling is finished, the single-phase Li in the ball milling tank is used1.3+xAl0.3-xMgxTi1.7(PO4)3Pouring out the slurry until single-phase Li is obtained1.3+xAl0.3-xMgxTi1.7(PO4)3After the absolute ethyl alcohol in the slurry is completely volatilized, the slurry is placed into an oven at 80 ℃ for secondary drying to obtain single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Material preparation; mixing single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Grinding the materials, and sieving with a 200-mesh sieve to obtain single-phase Li1.3+xAl0.3-xMgxTi1.7(PO4)3Finely grinding the particles.
8. The preparation method of the LAMTP single-phase ceramic wave-absorbing material of claim 3, wherein in S50, the sintering treatment specifically comprises the following steps: the single-phase Li obtained in S401.3+xAl0.3-xMgxTi1.7(PO4)3Placing the fine ground particles into a graphite mold, transferring the graphite mold into a plasma discharge sintering furnace, heating to 1000 ℃ at a heating rate of 100 ℃/min under the pressure condition of 30MPa, preserving heat for 5min, and cooling along with the furnace to obtain Li1.3+xAl0.3-xMgxTi1.7(PO4)3Single-phase ceramic wave-absorbing material.
9. The method for preparing LAMTP single-phase ceramic wave-absorbing material of claim 3, wherein the single-phase Li 40 is obtained from S401.3+xAl0.3-xMgxTi1.7(PO4)3The finely ground particles can also be used as raw materials of stealth coatings to carry out supersonic plasma spraying on the surfaces of objects needing stealth to obtain Li1.3+xAl0.3-xMgxTi1.7(PO4)3A single phase ceramic coating.
10. The application of the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material according to claim 1 or 2 in the field of wave-absorbing materials.
CN202010797301.7A 2020-08-10 2020-08-10 Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof Active CN111848151B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010797301.7A CN111848151B (en) 2020-08-10 2020-08-10 Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010797301.7A CN111848151B (en) 2020-08-10 2020-08-10 Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN111848151A true CN111848151A (en) 2020-10-30
CN111848151B CN111848151B (en) 2022-10-14

Family

ID=72972393

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010797301.7A Active CN111848151B (en) 2020-08-10 2020-08-10 Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN111848151B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114293126A (en) * 2021-12-03 2022-04-08 西安航空学院 LATP-TSC composite wave-absorbing coating and preparation method thereof
WO2024021822A1 (en) * 2022-07-27 2024-02-01 宜宾南木纳米科技有限公司 Magnesium-based solid electrolyte, preparation method therefor, and battery

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004095385A (en) * 2002-08-30 2004-03-25 Sumitomo Osaka Cement Co Ltd Method of manufacturing positive electrode material for lithium ion battery and lithium ion battery
US20040111874A1 (en) * 2002-12-16 2004-06-17 Kerstin Schierle-Arndt Preparation of a lithium ion conductor
CN101786873A (en) * 2009-01-22 2010-07-28 中国科学院上海硅酸盐研究所 Method for preparing electrolyte ceramic membrane of lithium ion battery
CN102648154A (en) * 2009-10-16 2012-08-22 南方化学股份公司 Phase-shift-free lithium aluminum titanium phosphate, and method for the production thereof and use thereof
CN102648153A (en) * 2009-10-16 2012-08-22 南方化学股份公司 Phase-pure lithium-aluminium-titanium phosphate and method for the production and use thereof
DE102012103409B3 (en) * 2012-04-19 2012-11-22 Karlsruher Institut für Technologie Preparing lithium-aluminum-titanium phosphate compounds useful for preparing solid-state electrolyte for lithium ion batteries, comprises e.g. providing aqueous solutions of lithium, aluminum, and phosphate salts, and forming sol
CN103441258A (en) * 2013-09-12 2013-12-11 兰州理工大学 Preparation method of carbon-coated porous lithium titanate powder
DE102012022606A1 (en) * 2012-11-19 2014-05-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Coated particulate electrode material, useful in lithium rechargeable batteries and/or double-layer capacitors, comprises particulate electrode material comprising lithium-intercalating and lithium deintercalating substances
JP2014096350A (en) * 2012-11-07 2014-05-22 Ngk Insulators Ltd Ceramic positive electrode-solid electrolyte assembly
CN106558665A (en) * 2015-09-25 2017-04-05 三星电子株式会社 Composite membrane, its preparation method, the cathode structure including which and the lithium secondary battery including cathode structure
WO2018062085A1 (en) * 2016-09-29 2018-04-05 Tdk株式会社 All solid-state lithium ion secondary battery
CN108075122A (en) * 2017-12-14 2018-05-25 电子科技大学 A kind of preparation method of lithium ion battery composite cathode material
US20180269483A1 (en) * 2017-03-20 2018-09-20 North Carolina Agricultural And Technical State University Prelithiated silicon particles for lithium ion batteries
CN109698339A (en) * 2018-12-28 2019-04-30 安徽科达铂锐能源材料有限公司 A kind of lithium titanate composite material and its preparation method and application
JP2019135720A (en) * 2014-05-19 2019-08-15 Tdk株式会社 Lithium ion secondary battery
CN110372367A (en) * 2019-07-12 2019-10-25 成都新柯力化工科技有限公司 A kind of lithium battery high-ductility ceramic solid electrolyte material and preparation method
CN110492172A (en) * 2019-08-20 2019-11-22 成都新柯力化工科技有限公司 A kind of lithium battery NASICON type solid electrolyte material and preparation method
CN110785876A (en) * 2017-07-10 2020-02-11 株式会社Lg化学 Positive electrode for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same
CN110862259A (en) * 2019-11-25 2020-03-06 贵州梅岭电源有限公司 High-conductivity solid electrolyte prepared by coprecipitation method
CN110885246A (en) * 2019-11-25 2020-03-17 贵州梅岭电源有限公司 High-conductivity solid electrolyte prepared by sol-gel method
CN111233458A (en) * 2020-02-17 2020-06-05 西南科技大学 Titanium aluminum lithium phosphate solid electrolyte material and preparation method thereof

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004095385A (en) * 2002-08-30 2004-03-25 Sumitomo Osaka Cement Co Ltd Method of manufacturing positive electrode material for lithium ion battery and lithium ion battery
US20040111874A1 (en) * 2002-12-16 2004-06-17 Kerstin Schierle-Arndt Preparation of a lithium ion conductor
CN101786873A (en) * 2009-01-22 2010-07-28 中国科学院上海硅酸盐研究所 Method for preparing electrolyte ceramic membrane of lithium ion battery
CN102648154A (en) * 2009-10-16 2012-08-22 南方化学股份公司 Phase-shift-free lithium aluminum titanium phosphate, and method for the production thereof and use thereof
CN102648153A (en) * 2009-10-16 2012-08-22 南方化学股份公司 Phase-pure lithium-aluminium-titanium phosphate and method for the production and use thereof
DE102012103409B3 (en) * 2012-04-19 2012-11-22 Karlsruher Institut für Technologie Preparing lithium-aluminum-titanium phosphate compounds useful for preparing solid-state electrolyte for lithium ion batteries, comprises e.g. providing aqueous solutions of lithium, aluminum, and phosphate salts, and forming sol
JP2014096350A (en) * 2012-11-07 2014-05-22 Ngk Insulators Ltd Ceramic positive electrode-solid electrolyte assembly
DE102012022606A1 (en) * 2012-11-19 2014-05-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Coated particulate electrode material, useful in lithium rechargeable batteries and/or double-layer capacitors, comprises particulate electrode material comprising lithium-intercalating and lithium deintercalating substances
CN103441258A (en) * 2013-09-12 2013-12-11 兰州理工大学 Preparation method of carbon-coated porous lithium titanate powder
JP2019135720A (en) * 2014-05-19 2019-08-15 Tdk株式会社 Lithium ion secondary battery
CN106558665A (en) * 2015-09-25 2017-04-05 三星电子株式会社 Composite membrane, its preparation method, the cathode structure including which and the lithium secondary battery including cathode structure
WO2018062085A1 (en) * 2016-09-29 2018-04-05 Tdk株式会社 All solid-state lithium ion secondary battery
US20180269483A1 (en) * 2017-03-20 2018-09-20 North Carolina Agricultural And Technical State University Prelithiated silicon particles for lithium ion batteries
CN110785876A (en) * 2017-07-10 2020-02-11 株式会社Lg化学 Positive electrode for lithium secondary battery, method for preparing same, and lithium secondary battery comprising same
CN108075122A (en) * 2017-12-14 2018-05-25 电子科技大学 A kind of preparation method of lithium ion battery composite cathode material
CN109698339A (en) * 2018-12-28 2019-04-30 安徽科达铂锐能源材料有限公司 A kind of lithium titanate composite material and its preparation method and application
CN110372367A (en) * 2019-07-12 2019-10-25 成都新柯力化工科技有限公司 A kind of lithium battery high-ductility ceramic solid electrolyte material and preparation method
CN110492172A (en) * 2019-08-20 2019-11-22 成都新柯力化工科技有限公司 A kind of lithium battery NASICON type solid electrolyte material and preparation method
CN110862259A (en) * 2019-11-25 2020-03-06 贵州梅岭电源有限公司 High-conductivity solid electrolyte prepared by coprecipitation method
CN110885246A (en) * 2019-11-25 2020-03-17 贵州梅岭电源有限公司 High-conductivity solid electrolyte prepared by sol-gel method
CN111233458A (en) * 2020-02-17 2020-06-05 西南科技大学 Titanium aluminum lithium phosphate solid electrolyte material and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEN DAN 等: "Divalent-Doped Li1.3Al0.3Ti1.7(PO4)(3) Ceramics with Enhanced Microwave Absorption Properties in the X-band", 《JOURNAL OF ELECTRONIC MATERIALS》 *
DAN CHEN等: ""NASICON-tpye Li1.3Al0.3Ti1.7(PO4)3 ceramics with frequency dispersion effect and microwave absorption properties in 8.2-12.4GHz"", 《JOURNAL OF MATERIALS SCIENCE: MATERIALS IN ELECTRONICS》 *
SYSOEVA, TS等: "Alkali (Alkaline-Earth) Metal, Aluminum, and Titanium Complex Orthophosphates: Synthesis and Characterization", 《SYNTHESIS AND PROPERTIES OF INORGANIC COMPOUNDS》 *
郑卫东等: "高岭土掺杂NASICON固体电解质及全固态电池性能", 《浙江大学学报（工学版）》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114293126A (en) * 2021-12-03 2022-04-08 西安航空学院 LATP-TSC composite wave-absorbing coating and preparation method thereof
WO2024021822A1 (en) * 2022-07-27 2024-02-01 宜宾南木纳米科技有限公司 Magnesium-based solid electrolyte, preparation method therefor, and battery

Also Published As

Publication number Publication date
CN111848151B (en) 2022-10-14

Similar Documents

Publication Publication Date Title
Ren et al. Novel Al 2 Mo 3 O 12-based temperature-stable microwave dielectric ceramics for LTCC applications
CN111848151B (en) Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof
CN110937892B (en) High-temperature absorbent, ultrathin high-temperature wave-absorbing material and preparation method thereof
Yi et al. Superionically conducting β′′-Al 2 O 3 thin films processed using flame synthesized nanopowders
Xu et al. Fabrication and performance of Ce0. 85Sm0. 15O1. 925–Fe2O3 electrolytes in IT-SOFCs
US6395381B1 (en) Vapor deposition material
CN109336592B (en) Zirconia ceramic bone implantation prosthesis and preparation method thereof
Wu et al. Effect of Ca2+ and Sr2+ doping on the microstructure and cell performance of samaria-doped ceria electrolytes used in solid oxide fuel cells
JPS58206003A (en) Low loss microwave dielectric material
Nasir et al. Li‐La‐Zr‐O Garnets with High Li‐Ion Conductivity and Air‐Stability by Microstructure‐Engineering
Absah et al. Bi2O3 and La10Si6O27 composite electrolyte for enhanced performance in solid oxide fuel cells
Zhang et al. Rapid fabrication of of Li7La3Zr2O12 solid electrolyte with enhanced lithium ionic conductivity by microwave sintering
JP2000353530A (en) MANUFACTURE OF NiO AND/OR Ni/YSZ COMPOSITE POWDER AND MANUFACTURE OF SOLID ELECTROLYTE FUEL CELL USING THEREOF
CN110862257A (en) Graphite ceramic closing resistor and preparation method thereof
CN114293126B (en) LATP-TSC composite wave-absorbing coating and preparation method thereof
CN112079631B (en) Low-dielectric LTCC material with near-zero temperature coefficient and preparation method thereof
Fang et al. Effects of Zr-Substitution on Microwave Dielectric Properties of Na 0.5 Nd 0.2 Sm 0.3 Ti 1− x Zr x O 3 Ceramics (x= 0.00∼ 0.30)
CN111574213B (en) Low-dielectric-constant LTCC material and preparation method thereof
Gao et al. Electrical Properties of Atmospheric Plasma-Sprayed La 10 (SiO 4) 6 O 3 Electrolyte Coatings
CN111774276A (en) Preparation method of calcium aluminate derivative thermal emission cathode crystal
CN112441830A (en) High-quality-factor yttrium-doped zirconia microwave dielectric ceramic material and preparation method thereof
Ren et al. Sintering behavior of 0.95 MgTiO3-0.05 CaTiO3 ceramics with high densification, high Q and enhanced mechanical properties for 5G massive MIMO technology: Effect of particle gradation
CN116283282B (en) Vanadium-based low-dielectric-constant microwave dielectric ceramic material and preparation method thereof
Pavzderin et al. Formation of a dense La (Sr) Fe (Ga) O3 interlayer at the electrolyte/porous cathode interface by magnetron sputtering and its effect on the cathode characteristics
Xiong et al. Highly enhanced Q× f value of Ca0. 61Nd0. 26TiO3 ceramics with SnO2 additive

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant