CN114606470B - Lithium phosphate tube target and integrally formed preparation method thereof - Google Patents
Lithium phosphate tube target and integrally formed preparation method thereof Download PDFInfo
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- CN114606470B CN114606470B CN202210239702.XA CN202210239702A CN114606470B CN 114606470 B CN114606470 B CN 114606470B CN 202210239702 A CN202210239702 A CN 202210239702A CN 114606470 B CN114606470 B CN 114606470B
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- 229910001386 lithium phosphate Inorganic materials 0.000 title claims abstract description 109
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 47
- 238000007872 degassing Methods 0.000 claims abstract description 40
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 34
- 238000011049 filling Methods 0.000 claims abstract description 16
- 238000003466 welding Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 9
- 229910001200 Ferrotitanium Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 239000010439 graphite Substances 0.000 claims description 40
- 229910002804 graphite Inorganic materials 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000003754 machining Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005056 compaction Methods 0.000 claims description 5
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 4
- 239000010962 carbon steel Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052744 lithium Inorganic materials 0.000 abstract description 7
- 238000005429 filling process Methods 0.000 abstract description 6
- 238000005204 segregation Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 229910012305 LiPON Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000013077 target material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000005477 sputtering target Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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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
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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
- C04B35/645—Pressure sintering
- C04B35/6455—Hot isostatic pressing
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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Abstract
The invention relates to a lithium phosphate tube target and an integrally formed preparation method thereof, belongs to the technical field of all-solid-state lithium batteries, and solves the problem of low utilization rate of planar Li 3PO4 targets in the prior art. The preparation method comprises the steps of filling lithium phosphate powder into a sheath, and vibrating and compacting while filling in the filling process; sealing and degassing the filled sheath, wherein the degassing temperature is 500-700 ℃; after sealing the welding degassing port, performing hot isostatic pressing treatment; and removing part of the structure of the sheath after hot isostatic pressing to obtain the lithium phosphate tube target. The lithium phosphate tube target comprises a supporting inner tube and an outer tube, wherein the supporting inner tube is made of pure titanium or stainless steel; the outer tube is lithium phosphate. The lithium phosphate tube prepared by the preparation method has the advantages of high purity, high density, fine grains, uniform components, no visible segregation, tight combination of the outer tube and the inner supporting tube, and suitability for large-scale production.
Description
Technical Field
The invention relates to the technical field of all-solid-state lithium batteries, in particular to a lithium phosphate tube target and an integrally formed preparation method thereof.
Background
The all-solid-state thin film lithium battery has the advantages of small size, light weight, high safety, high stability, high specific volume, high power density, low self-discharge rate, excellent charge-discharge cycle performance, high freedom degree of shape and size design and the like, and is an important development direction of the battery technology in the future. Solid electrolyte films as a core technology are the focus of current technological attack. LiPON has good thermal stability and chemical stability, can overcome the problems of growth of lithium dendrite, continuous thickening of passivation layer, low cycle life of battery and the like as an electrolyte film, and is the electrolyte film most widely applied in the current research of all-solid-state thin-film lithium batteries. In addition, the LiPON film is beneficial to improving the ion conductivity in the solid electrolyte due to the anisotropic amorphous structure, and the material contains lithium ions, so that the content of the lithium ions in the electrolyte can be improved on one hand, and the penetration of the lithium ions is facilitated on the other hand, so that the LiPON film is an important research object of a plurality of researchers.
The performance of the solid-state lithium battery film directly determines the capacity and the service life of the battery, the LiPON solid-state electrolyte film is generally prepared by taking nitrogen as a reaction gas through a radio frequency magnetron sputtering method through a Li 3PO4 target, and whether to prepare a high-quality Li 3PO4 sputtering target is an extremely important factor besides controlling various process conditions for preparing the film. In the prior art, the Li 3PO4 target is mostly a planar target, the utilization rate of the planar target is low, and the utilization rate is only about 30%.
Disclosure of Invention
In view of the above analysis, the embodiment of the invention aims to provide a lithium phosphate tube target and an integrated forming preparation method thereof, which are used for solving the problem of low utilization rate of planar Li 3PO4 targets in the prior art.
The invention discloses a preparation method of a lithium phosphate tube target, which comprises the steps of filling lithium phosphate powder into a sheath, and vibrating and compacting while filling in the filling process; degassing the charged sheath at 500-700 ℃; performing hot isostatic pressing treatment after degassing; and removing part of the structure of the sheath after hot isostatic pressing to obtain the lithium phosphate tube target.
Further, the method comprises the following steps:
step 1: selecting battery grade lithium phosphate powder, wherein the purity of the lithium phosphate powder is 99.9%, and the powder can pass through a 160-mesh sieve;
step 2: filling lithium phosphate powder into a hot isostatic pressing sheath, vibrating the filled sheath on a vibration platform, and sealing and welding an upper cover of the sheath with the inner wall of the sheath and the outer wall of the sheath; the package comprises a package outer wall, first graphite paper, a cavity, a package inner wall, second graphite paper and a control column from outside to inside; filling lithium phosphate powder into the cavity;
Step 3: degassing the filled sheath, wherein the degassing temperature is 500-700 ℃, the degassing vacuum degree is less than or equal to 2 multiplied by 10 -3 Pa, preserving heat, cooling along with a furnace, and sealing and welding a degassing port;
Step 4: placing the sheath into hot isostatic pressing equipment, performing hot isostatic pressing treatment, and cooling along with a furnace after the hot isostatic pressing treatment;
Step 5: and (3) machining to remove the outer wall of the sheath, the first graphite paper, the second graphite paper and the control column, so as to obtain a lithium phosphate tube target blank, and machining the blank to obtain the integrally formed lithium phosphate tube target.
Further, in the step 3, the temperature is kept for 1 to 6 hours.
Further, in the step 4, the hot isostatic pressing treatment is carried out for 2 to 6 hours under the temperature of 700 to 900 ℃ and the pressure of 100 to 200 MPa.
Further, in the step2, the relative density of the lithium phosphate powder after charging compaction is ensured to be more than or equal to 50 percent.
Further, the outer wall of the sheath is made of carbon steel, stainless steel or pure titanium, and the inner wall of the sheath is made of pure titanium or stainless steel.
Further, the thickness of the outer wall of the sheath is 2-4 mm.
Further, the degassing temperature is 550 to 650 ℃.
Further, the thickness of the final tube target is less than 6mm, and in step 2, the second graphite paper and the control column are not placed.
The invention also provides a lithium phosphate tube target which is prepared by adopting the preparation method, and comprises a supporting inner tube and an outer tube, wherein the supporting inner tube is made of pure titanium or stainless steel; the outer tube is lithium phosphate.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. According to the preparation method of the integrated forming of the lithium phosphate tube target, the lithium phosphate powder is filled into the sheath, and the filling process is carried out while vibrating compaction, so that the filling density can reach more than 50% of the theoretical density, the upper cover of the sheath, the inner wall and the outer wall of the sheath are sealed and welded, then the degassing port is sealed and welded, and the integrated forming of the lithium phosphate tube target is carried out by adopting a hot isostatic pressing method, so that the lithium phosphate tube target is obtained; the lithium phosphate tube obtained by the invention has the advantages of high purity, high density, fine crystal grains, uniform components, no visible segregation, and tight combination of the outer tube and the supporting inner tube.
2. The preparation method for integrally forming the lithium phosphate tube target has the advantages of few procedures and simple process, and can be suitable for large-scale production.
3. The lithium phosphate tube target provided by the invention can obtain a film with excellent performance through a proper magnetron sputtering process, and the energy storage capacity and the cycle number of the solid-state battery are improved; the utilization rate of the lithium phosphate tube target provided by the invention can reach more than 70% when the lithium phosphate tube target is used.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
FIG. 1 is a schematic cross-sectional view of a jacket according to an embodiment of the present invention;
FIG. 2 is a DSC curve of lithium phosphate powder provided in an embodiment of the present invention;
FIG. 3 is a thermogravimetric test curve of a lithium phosphate powder according to an embodiment of the present invention;
FIG. 4 is an analysis of the interface energy spectrum of the outer tube and the support inner tube of the lithium phosphate tube target provided by the embodiment of the invention;
Fig. 5 is an SEM analysis of a fracture of a lithium phosphate tube target according to an embodiment of the present invention.
Reference numerals
1-Sheath outer wall, 2-first graphite paper, 3-cavity, 4-sheath inner wall, 5-second graphite paper and 6-control column.
Detailed Description
The following detailed description of preferred embodiments of the application is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the application, are used to explain the principles of the application and are not intended to limit the scope of the application.
At present, most Li 3PO4 sputtering targets are plane targets, and the utilization rate of the plane targets is low, and only about 30% of the utilization rate is available. Therefore, the inventor has provided a lithium phosphate tube target (namely a tubular target material) through long-term intensive research, the tube target is composed of a supporting inner tube and an outer tube, the supporting inner tube plays a role in supporting and fixing, and the supporting inner tube is made of pure titanium or stainless steel; the outer tube is Li 3PO4 which is a material required by sputtering to prepare a film, and the utilization rate of the tubular target can reach 70%.
The inventors found in the study that the lithium phosphate material has a low density, the relative density is only 2.537g/cm 3, the powder shape is non-spherical, the powder is irregular and the loose density is low, a small amount of binder is often added during compression molding or cold molding, and even though the later degumming treatment can be carried out, a small amount of binder remains to influence the quality of the target material.
The invention discloses a preparation method for integrally forming a lithium phosphate tube target, which comprises the steps of filling lithium phosphate powder into a sheath, and vibrating and compacting while filling in the filling process; carrying out degassing treatment on the filled sheath seal welding feed inlet, wherein the degassing temperature is 500-700 ℃; after sealing the welding degassing port, performing hot isostatic pressing treatment; and removing part of the structure of the sheath after hot isostatic pressing to obtain the lithium phosphate tube target.
Specifically, the lithium phosphate tube target consists of two parts, namely a supporting inner tube and an outer tube, wherein the supporting inner tube plays a role in supporting and fixing, and the outer tube is Li 3PO4.
Compared with the prior art, the preparation method of the integrated forming of the lithium phosphate tube target ensures that the filling density can reach more than 50% of the theoretical density by filling lithium phosphate powder into the sheath and vibrating and compacting the lithium phosphate powder while filling in the filling process, then the upper cover of the sheath, the inner wall of the sheath and the outer wall of the sheath are sealed and welded, the sheath is degassed, then the degassing port is sealed and welded, and then the integrated forming of the lithium phosphate tube target is realized by adopting a hot isostatic pressing method, wherein the degassing is used for extracting the existing gas in the sheath, and simultaneously extracting the water adsorbed on the surface of lithium phosphate and dissociated, so that the water vapor generated in the lithium phosphate target material in the subsequent hot isostatic pressing treatment process is prevented, and the final density of the tube target is influenced; the lithium phosphate tube obtained by the invention has the advantages of high purity, high density, fine crystal grains, uniform components, no visible segregation, and tight combination of the outer tube and the supporting inner tube.
Specifically, the preparation method for integrally forming the lithium phosphate tube target comprises the following steps:
step 1: selecting battery grade lithium phosphate powder, wherein the purity of the lithium phosphate powder is 99.9%, and the powder can pass through a 160-mesh sieve (namely, the particle size of the powder is less than 97 mu m);
Step 2: filling lithium phosphate powder into a hot isostatic pressing sheath, compacting while filling in the filling process, compacting the filled sheath on a vibration platform, and sealing and welding an upper cover of the sheath with the inner wall and the outer wall of the sheath; the lithium phosphate powder is filled in the cavity 3, wherein the sheath comprises a sheath outer wall 1, first graphite paper 2, a cavity 3, a sheath inner wall 4, second graphite paper 5 and a control column 6 from outside to inside;
Step 3: degassing the filled sheath, wherein the degassing temperature is 500-700 ℃, the degassing vacuum degree is less than or equal to 2 multiplied by 10 -3 Pa, the temperature is kept for 1-6 hours, and the degassing port is sealed and welded after natural cooling;
step 4: placing the sheath into hot isostatic pressing equipment, preserving heat and pressure for 2-6 hours at the temperature of 700-900 ℃ and the pressure of 100-200 MPa, and cooling along with a furnace;
step 5: and (3) machining to remove the outer wall 1 of the sheath, the first graphite paper 2, the second graphite paper 5 and the control column 6, obtaining the inner wall 4 of the sheath as a supporting inner tube, taking the outer part of the lithium phosphate tube target blank as the target outer tube, and machining the blank to obtain the integrally formed lithium phosphate tube target.
Specifically, in the step 2, as shown in fig. 1, the sheath includes a sheath outer wall 1, a first graphite paper 2, a cavity 3, a sheath inner wall 4, a second graphite paper 5 and a control column 6; the sheath also comprises an upper cover and a lower cover; cutting the first graphite paper 2 according to the inner circumferential length of the outer wall 1 of the jacket before loading, placing the first graphite paper 2 on the inner side of the outer wall 1 of the jacket, fixing the first graphite paper 2, and loading lithium phosphate powder into a cavity 3 in the jacket; the lithium phosphate powder is compacted while being filled in the charging process, so that the relative density of the lithium phosphate powder after the charging compaction is more than or equal to 50 percent. In this step, the first graphite paper 2 is placed between the outer wall 1 of the sheath and the lithium phosphate powder, so as to facilitate the separation of the materials on both sides of the first graphite paper 2 after the hot isostatic pressing is completed.
Specifically, in the above step 3, considering that Li 3PO4 is slightly soluble in water, li 3PO4 powder is liable to absorb moisture, and H 2 O molecules adsorbed on the surface of Li 3PO4 after moisture absorption may also be dissociated to generate OH - and H +, which are adsorbed on the surface of Li 3PO4 together. H 2 O cannot be removed by both evaporation and boiling by heating to boiling point (100 ℃ at normal pressure) after dissociation, so the Li 3PO4 sputtering target should suppress moisture absorption as much as possible during production and subsequent storage. Therefore, in the above step 3, the moisture in the lithium phosphate can be removed by controlling the degassing temperature.
Specifically, in the step 3, if the degassing temperature is too low, the water dissociated from the hygroscopic lithium phosphate cannot be removed, if the degassing temperature is too high, the powder is seriously pre-sintered, and the grains of the target may grow. Therefore, the degassing temperature is controlled to 500 to 700 ℃.
Specifically, in the step 3, the degassing vacuum degree is controlled to be less than or equal to 2 multiplied by 10 -3 Pa.
Specifically, in the step 3, the heat preservation time is too short, and the water adsorbed on the surface of the lithium phosphate and dissociated cannot be completely removed. Therefore, the heat preservation is controlled for 1 to 6 hours. After the heat preservation time reaches the requirement, the degassing port is completely welded, and no air leakage can be caused.
In the step 4, the control column 6 is disposed on the central axis of the jacket, and the second graphite paper 5 is disposed between the control column 6 and the inner wall 4 of the jacket. The function of the control column 6 is to prevent the sheath from shrinking in the direction of the center, and the final size of the product is unqualified. The second graphite paper 5 is used for facilitating the separation of the control column 6 from the inner wall 4 of the jacket.
In the step 2, if the lithium phosphate tube target layer is made thinner, for example, the thickness is smaller than 6mm, the control of the center of the tube target is not required, and the second graphite paper 5 and the control column 6 may not be placed.
Specifically, in the step 4, the density is higher along with the increase of the hot isostatic pressing temperature, but the temperature cannot be increased limitlessly, the grains grow up at too high temperature, and the target performance is poor, so the temperature is controlled to be 700-900 ℃.
Specifically, in the step 4, the sealed sheath is placed in a working tool of the hot isostatic pressing device, the hot isostatic pressing device is vacuumized, then argon is pre-filled, and the heating is performed according to a set heating program. The pressure in the cavity of the hot isostatic pressing machine is 100 MPa-200 MPa; the heat preservation and pressure maintaining time is controlled to be 2-6 hours according to the size of the workpiece. And after the heat preservation is finished, cooling along with the furnace, and finishing the hot isostatic pressing operation process.
Specifically, in the step 4, under the high temperature effect of the hot isostatic pressing device, the mechanical strength of the sheath material is reduced along with the temperature rise, the pressure difference between the inner part and the outer part of the sheath wall promotes the sheath to shrink, the pressure is conducted to the internal target powder, the powder is sintered and densified, and the relative density of the target is increased from about 50% after compaction to more than 98% of hot isostatic pressing.
Specifically, in the step2, the inner wall 4 of the sheath needs to be used as a supporting inner tube in the later stage, and considering that the supporting inner tube needs to be a carrying tube suitable for a lithium phosphate magnetron sputtering target, the carrying tube needs to be nonmagnetic or weakly magnetic, so that the inner wall 4 of the sheath is made of pure titanium or stainless steel. The material selection of the outer wall 1 of the sheath is mainly considered from the aspects of production cost and welding feasibility with the upper cover and the lower cover of the sheath, so that the material of the outer wall 1 of the sheath can be carbon steel, stainless steel or pure titanium.
Specifically, the thickness of the outer wall 1 of the sheath is too large, so that the welding is difficult and uneconomical; too small, difficult to weld, easy to weld leakage, and affects the yield. Therefore, the thickness of the outer wall of the sheath is controlled to be 2-4 mm; the thickness of the inner wall 4 of the jacket can be freely set according to the requirement of the tube target bearing, for example, the thickness of the inner wall 4 of the jacket can be controlled to be 3-10 mm.
Specifically, the material of the control column 6 is graphite column or carbon steel, and the control column 6 can be made into a solid structure or a thick-wall pipe with a wall thickness of more than 15 mm.
Specifically, if the control column 6 is graphite, the second graphite paper 5 may not be placed.
Specifically, the first graphite paper 2 and the second graphite paper 5 are used for facilitating the separation of materials on two sides of the graphite paper. When the graphite paper is too thick, the graphite paper is easy to crack when cut and enclosed into a circumferential structure; too thin, the graphite paper does not significantly aid in detachment of the sides. Therefore, the thickness of the graphite paper is controlled to be about 0.05 to 0.2mm.
Specifically, the purity of the obtained lithium phosphate tube target is 99.9% through chemical component analysis and test, and the measured density is more than 98%.
Specifically, the lithium phosphate tube target obtained in the step 5 has a fine grain size, which is substantially the same as the powder size in the step 1.
The preparation method for integrally forming the lithium phosphate tube target has the advantages of few procedures and simple process, and the prepared lithium phosphate tube target has high density, high purity and small grain size, and has uniform components and no visible segregation; the support inner tube and the outer tube of the tube target are integrally formed, the whole contact surface is comprehensively connected through interdiffusion, the connection strength is high, the connection is stable, and the requirement of the high-performance solid-state lithium battery on the high-quality lithium phosphate tube target is met. The lithium phosphate tube target prepared by the invention can obtain a film with excellent performance through a proper magnetron sputtering process, and the energy storage capacity and the cycle times of the solid-state battery are improved. The utilization rate of the lithium phosphate tube target can reach more than 70% when the lithium phosphate tube target is used.
Example 1
The embodiment provides a preparation method for integrally forming a lithium phosphate tube target, which comprises the following steps:
step 1: selecting battery grade lithium phosphate powder, wherein the purity of the lithium phosphate powder is 99.9%, and the powder can pass through a 160-mesh sieve (namely, the particle size of the powder is less than 97 mu m);
Step 2: filling lithium phosphate powder into a hot isostatic pressing sheath, vibrating the filled sheath on a vibration platform, and sealing and welding an upper cover of the sheath with the inner wall of the sheath and the outer wall of the sheath; the package comprises a package outer wall 1, first graphite paper 2, a cavity 3, a package inner wall 4, second graphite paper 5 and a control column 6 from outside to inside; lithium phosphate powder is filled into the cavity 3;
Step 3: degassing the filled sheath, wherein the degassing temperature is 550-650 ℃, the degassing vacuum degree is less than or equal to 2 multiplied by 10 -3 Pa, the temperature is kept for 1-6 hours, and the degassing port is sealed and welded after natural cooling;
step 4: placing the sheath into hot isostatic pressing equipment, preserving heat and pressure for 2-6 hours at the temperature of 700-900 ℃ and the pressure of 100-200 MPa, and cooling along with a furnace;
step 5: and (3) machining to remove the outer wall 1 of the sheath, the first graphite paper 2, the second graphite paper 5 and the control column 6, obtaining the inner wall 4 of the sheath as a supporting inner tube, taking the outer part of the lithium phosphate tube target blank as the target outer tube, and machining the blank to obtain the integrally formed lithium phosphate tube target.
Specifically, lithium phosphate tube targets of different sizes in 4 were prepared in this example, and specific process parameters are shown in tables 1 and 2 below.
Table 1 parameters relating to the envelope
Table 2 parameters relating to the envelope
The DSC curve of the lithium phosphate powder in example 1 is shown in FIG. 2, and the lithium phosphate powder has exothermic peaks between 480 ℃ and 500 ℃ through DSC test; as shown in the thermal gravimetric test curve of the lithium phosphate powder in FIG. 3, the thermal gravimetric analysis test result shows that the lithium phosphate powder sample has an exothermic peak at 499.5 ℃, the weight of the sample is continuously lost before 200-800 ℃, and the slope of the thermal gravimetric curve increases at the position of the exothermic peak, so that the weight loss is aggravated. It is estimated from DSC test results and thermogravimetric test results that lithium phosphate undergoes dehydration reaction at a temperature of 490 ℃ or higher. In the conventional sheath manufacturing process, the degassing temperature is 400-480 ℃, a small amount of water still remains in the sample at the moment, and when the heating temperature reaches the dehydration reaction temperature in the subsequent hot isostatic pressing sintering, gas is generated in dehydration, so that the final density of the target is affected.
Fig. 4 shows energy spectrum analysis of the interface between the outer tube and the supporting inner tube of the lithium phosphate tube target, and the energy spectrum analysis shows that the outer tube and the supporting inner tube are not only physically pressed together, but also are in diffusion reaction at the connecting interface of the two materials, so that metallurgical bonding is formed, and the connection is firm.
Fig. 5 shows SEM analysis of the fracture of the lithium phosphate tube target, no obvious visible cavity is formed on the surface of the target, the crystal grains are tightly combined, the granularity distribution is uniform, and the density of the target in all samples is more than 98%.
The lithium phosphate tube target can obtain a film with excellent performance through a proper magnetron sputtering process, and the energy storage capacity and the cycle times of the solid-state battery are improved.
Comparative example
The comparative example provides a method for preparing a lithium phosphate tube target by integrally molding, which has the steps basically the same as those of example 1, except that:
5#: the degassing temperature in the step 3 is 450 ℃, the degassing vacuum degree is 2 multiplied by 10 -3 Pa, the hot isostatic pressing process is 800-130 MPa-3h, and the relative density of the lithium phosphate tube target obtained in the comparative example is 94.5%.
Compared with the comparative example, the embodiment 1 of the invention has high degassing temperature, and the moisture adsorbed on the surface of the lithium phosphate can be removed through the degassing procedure, so that the moisture decomposition can not occur in the subsequent hot isostatic pressing procedure, and the density of the target material is affected. Therefore, the lithium phosphate tube target prepared by the method for integrally forming the lithium phosphate tube target has the advantages of high density, high purity, fine grain size, uniform composition of the lithium phosphate tube target and no visible segregation; the support inner tube and the outer tube of the tube target are integrally formed, and the whole contact surface is comprehensively connected through interdiffusion, so that the connection strength is high, and the connection is stable.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (8)
1. A method for preparing a lithium phosphate tube target, the method comprising the steps of:
step 1: selecting battery grade lithium phosphate powder, wherein the purity of the lithium phosphate powder is 99.9%, and the powder can pass through a 160-mesh sieve;
Step 2: filling lithium phosphate powder into a hot isostatic pressing sheath, vibrating the filled sheath on a vibration platform, and sealing and welding an upper cover of the sheath with the inner wall of the sheath and the outer wall of the sheath; the package comprises a package outer wall (1), first graphite paper (2), a cavity (3), a package inner wall (4), second graphite paper (5) and a control column (6) from outside to inside; lithium phosphate powder is filled into the cavity (3);
Step 3: degassing the filled sheath, wherein the degassing temperature is 500-700 ℃, the degassing vacuum degree is less than or equal to 2 multiplied by 10 - 3 Pa, preserving heat, cooling along with a furnace, and sealing and welding a degassing port;
Step 4: placing the sheath into hot isostatic pressing equipment, performing hot isostatic pressing treatment, and cooling along with a furnace after the hot isostatic pressing treatment;
Step 5: machining to remove the outer wall (1) of the sheath, the first graphite paper (2), the second graphite paper (5) and the control column (6) to obtain a lithium phosphate tube target blank, and machining the blank to obtain an integrally formed lithium phosphate tube target;
in the step 2, the relative density of the lithium phosphate powder after charging compaction is ensured to be more than or equal to 50%;
In the step 3, preserving heat for 1-6 hours; the deaeration can extract the water adsorbed on the surface of the lithium phosphate and dissociated;
in the step 4, the hot isostatic pressing treatment is carried out for 2 to 6 hours under the temperature of 720 to 900 ℃ and the pressure of 100 to 200 MPa;
The density of the obtained lithium phosphate tube target is more than 98%, and the utilization rate of the lithium phosphate tube target is more than 70% when the lithium phosphate tube target is used.
2. The method according to claim 1, wherein in the step 3, the temperature is maintained for 1 to 4 hours.
3. The method according to claim 1, wherein in the step4, the pressure is 130 to 200MPa.
4. The preparation method according to claim 1, wherein the material of the outer wall (1) of the sheath is carbon steel, stainless steel or pure titanium, and the material of the inner wall (4) of the sheath is pure titanium or stainless steel.
5. The method according to claim 1, characterized in that the thickness of the jacket outer wall (1) is 2-4 mm.
6. The method according to claim 1, wherein the degassing temperature is 550 to 650 ℃.
7. The method according to claim 1, wherein the final tube target has a thickness of less than 6mm, and wherein in step 2, the second graphite paper (5) and the control column (6) are not placed.
8. A lithium phosphate tube target, which is characterized in that the lithium phosphate tube target is prepared by adopting the preparation method of any one of claims 1-7, and comprises a supporting inner tube and an outer tube, wherein the supporting inner tube is made of pure titanium or stainless steel; the outer tube is lithium phosphate.
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