CN102779656A - Sintering method for lowering leakage current value of tantalum capacitor - Google Patents
Sintering method for lowering leakage current value of tantalum capacitor Download PDFInfo
- Publication number
- CN102779656A CN102779656A CN2012102369825A CN201210236982A CN102779656A CN 102779656 A CN102779656 A CN 102779656A CN 2012102369825 A CN2012102369825 A CN 2012102369825A CN 201210236982 A CN201210236982 A CN 201210236982A CN 102779656 A CN102779656 A CN 102779656A
- Authority
- CN
- China
- Prior art keywords
- sintering
- tantalum
- leakage current
- current value
- temperature
- 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.)
- Pending
Links
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 80
- 238000005245 sintering Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003990 capacitor Substances 0.000 title claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
- 239000001301 oxygen Substances 0.000 abstract description 14
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract 1
- 238000011010 flushing procedure Methods 0.000 abstract 1
- 238000009766 low-temperature sintering Methods 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 150000003481 tantalum Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
The invention discloses a sintering method for lowering the leakage current value of a tantalum capacitor. The method comprises the following steps of: putting a metal taken as a deoxidant and a pressed and sintered tantalum block into a vacuum sintering furnace for sintering, wherein the metal has low melting point, and the metal or an oxide thereof easily reacts with water or an acid; in a sintering process, the vacuum degree is always more than 2*10<-3> Torr, the sintering temperature is 700-1,170 DEG C, the weight ratio of the tantalum block to the deoxidant is 1:0.001-1:0.08, heat preserving time after the sintering temperature is 1-9 hours, and magnesium is taken as the deoxidant; and deoxidizing, sintering, cooling to the room temperature in a vacuum state, putting the tantalum block into a diluted acid for soaking for 30 minutes to remove residual metal deoxidant and an oxide of the deoxidant on the surface of the tantalum block, and flushing with deionized water for 3-4 times. Oxygen impurities are removed under a low-temperature sintering situation by performing secondary sintering on the tantalum block, so that the purity of the tantalum block is increased effectively, and the leakage current value of a product is lowered by over 30 percent.
Description
Technical field
The present invention relates to capacitor manufacturing technology field, particularly a kind of sintering method that reduces the tantalum capacitor leakage current value.
Background technology
In recent years; Along with complete electronic set is fast-developing to the direction of miniaturization, digitlization, high frequencyization; Tantalum capacitor has been proposed under not reducing original specification requirement or developing skill the prerequisite that requires, to have higher operating voltage, bigger static capacity, littler volume.Need use the increasingly high tantalum powder of specific volume to carry out the production of tantalum capacitor, and specific volume is high more, the particle of tantalum powder is thin more for this reason, and the adsorption capacity of tantalum powder is also strong more, so oxidative phenomena impurity serious, absorption is also more.The deielectric-coating that carries out the tantalum piece in this case adds man-hour, can form fault in oxidized position, make the deielectric-coating fracture of oxidized position, and the tantalum piece that obtains parameter when carrying out the leakage current test exceeds requirement and defective.Numerous for this reason tantalum capacitor manufacturers has carried out a lot of explorations to the process that how to reduce tantalum piece leakage current, as takes to change sintering curre, behind sintering, ripe article surface state is carried out technologies such as Passivation Treatment.The enforcement that these are technological; Reduced the leakage current value of tantalum piece to a certain extent; But the other technologies index of capacitor such as equivalent series resistance (ESR), loss value, with one or several variation in the indexs such as temperature change value, and implement control difficulty and the production cost that above-mentioned technology has also increased production process.
Summary of the invention
To the problems referred to above; The present invention discloses a kind of sintering method that reduces the tantalum capacitor leakage current value; Lower and itself or oxide are prone to be placed in the same container as deoxidier and tantalum piece through press forming and sintering with the metal of water or acid reaction with fusing point; Deoxygenation under the high-temperature vacuum state of vacuum sintering furnace, thus tantalum piece fault eliminated, reduce the leakage current value of the capacitor that uses this tantalum piece making.
For guaranteeing that deoxidier fully reduces the oxidized part of tantalum piece, described vacuum sintering furnace is in sintering process, and vacuum degree is all the time greater than 2 * 10
-3Torr.
Described sintering temperature is between 700 ~ 1170 ℃, especially between 900 ~ 1000 ℃.
Make full use of and do not produce too much impurity for what guarantee deoxidier, the weight ratio of tantalum piece and deoxidier is 1:0.001 ~ 1:0.08, especially 1:0.009 ~ 1:0.06.
Because the tantalum piece had passed through press forming and sintering before adopting the inventive method sintering, become deielectric-coating for thoroughly removing the oxidized portion novel crystalline form of laying equal stress on, temperature retention time is 1 ~ 9 hour in the method, especially 5 ~ 7 hours.
Enliven metal such as sodium, magnesium, aluminium etc. as the deoxidier comparison that experimentizes, with the best results of magnesium through selecting difference for use as deoxidier.
Accomplish the deoxidation sintering and after vacuum state drops to room temperature,, the tantalum piece is put into diluted acid immersion 30 minutes, use deionized water rinsing again 3～4 times for the metal deoxidier of removing tantalum piece remained on surface and the oxide of this deoxidier.Soaked 30 minutes with dilute acid soln again with the tantalum piece that deionized water soaks for this operation, take out in the baking oven that is put into 150 ℃ then and dry by the fire more than 30 minutes.
The present invention is through carrying out double sintering to the tantalum piece; Under the situation of lower temperature sintering, increase the means of removing oxygen impurities; Oxygen impurities content in the tantalum piece can reduce to about 50% of oxygen impurities content in the Ta powder, improves the purity of tantalum piece effectively, and the leakage current value of product reduces more than 30%.
Description of drawings
Fig. 1 is the sintering curre figure of the inventive method.
Embodiment
The sintering method of reduction tantalum capacitor leakage current value according to the invention; Be that lower and itself or oxide are prone to be placed on same container for example in the tantalum crucible with the metal of water or acid reaction as deoxidier with through the tantalum piece behind the press forming sintering with fusing point; Deoxygenation under the high-temperature vacuum state of vacuum sintering furnace; Utilize this tantalum piece to process tantalum capacitor, can effectively reduce the leakage current value of tantalum capacitor.
For guaranteeing that deoxidier fully reduces the oxidized part of tantalum piece, in the sintering process in vacuum sintering furnace, sintering limit, limit vacuumizes, and makes vacuum degree all the time greater than 2x10
-3Torr.
Sintering temperature T as shown in Figure 1 is between 700 ~ 1170 ℃, especially between 900 ~ 1000 ℃.Because the tantalum piece had passed through press forming and sintering before adopting the inventive method sintering, in the temperature-rise period of this method t1 time period, heating rate is not required; Because the fusing point of metal deoxidier is well below the sintering temperature of tantalum piece, thus in the temperature-rise period of t1 time period the metal deoxidier at first reach vapourizing temperature and with the tantalum piece in contained oxygen react.For making tantalum piece progress one abundant deoxidation, after reaching sintering temperature, be incubated, temperature retention time section t2 is 1 ~ 9 hour, especially 5 ~ 7 hours.
Make full use of and do not produce too much impurity for what guarantee deoxidier; The applicant explores the weight ratio of tantalum piece and deoxidier; Calculate and the experiment trial through a large amount of theory analysises, science; The weight ratio of confirming tantalum piece and deoxidier is 1:0.001 ~ 1:0.08, especially 1:0.009 ~ 1:0.06, and concrete ratio 1:0.007 therebetween, 1:0.01,1:0.03,1:0.05 particularly 1:0.06 obviously are superior to other ratios.
Through selecting for use different metal such as sodium, magnesium, aluminium etc. of enlivening as the deoxidier comparison that experimentizes, with the best results of magnesium as deoxidier.
Accomplish the deoxidation sintering and after vacuum state drops to room temperature,, the tantalum piece is put into diluted acid immersion 30 minutes, use deionized water rinsing again 3～4 times for the metal deoxidier of removing tantalum piece remained on surface and the oxide of this deoxidier.Soaked 30 minutes with dilute acid soln again with the tantalum piece that deionized water soaks for this operation, take out in the baking oven that is put into 150 ℃ then and dry by the fire more than 30 minutes.
For confirming the beneficial effect of sintering method of the present invention, the applicant has carried out confirmatory experiment.
Confirmatory experiment 1:
With CA45 type 50V10 μ F is example: using the CV value is that the tantalum powder pressed density of 3500 μ F.V/g is 6.5g/cm
3Be of a size of the tantalum piece of 5.0 * 3.8 * 4.0mm, by pressing method deoxidation of the present invention behind the prior art sintering, the weight ratio of tantalum piece and deoxidier adopts 1:0.06, is evacuated to 2 * 10
-4Torr also remains this vacuum degree, and temperature rises to 1000 ℃ of insulations 6 hours.The metal deoxidier of removing tantalum piece remained on surface by method of the present invention with and oxide after, oxygen content in the tantalum piece after the sampling measurement deoxidation, oxygen content value as shown in the table is reduced between 765ppm～829ppm.Accomplish tantalum capacitor production according to existing technology again, leakage current measurement is carried out in sampling, reduces to 0.29 ~ 0.35 μ A like its leakage current value of following table.
Confirmatory experiment 2:
With CA45 type 35V10 μ F is example: using the CV value is that the tantalum powder pressed density of 8000 μ F.V/g is 5.5g/cm
3Be of a size of the tantalum piece of 4.0 * 3.5 * 2.3mm, by pressing method deoxidation of the present invention behind the prior art sintering, the weight ratio of tantalum piece and deoxidier adopts 1:0.01, is evacuated to 7 * 10
-4Torr also remains this vacuum degree, and temperature rises to 900 ℃ of insulations 2.5 hours.The metal deoxidier of removing tantalum piece remained on surface by method of the present invention with and oxide after, oxygen content in the tantalum piece after the sampling measurement deoxidation, oxygen content value as shown in the table is reduced between 1050ppm～1360ppm.Accomplish tantalum capacitor production according to existing technology again, leakage current measurement is carried out in sampling, reduces to 0.19 ~ 0.24 μ A like its leakage current value of following table.
Confirmatory experiment 3:
With CA45 type 6.3V100 μ F is example: using the CV value is that the tantalum powder pressed density of 100000 μ F.V/g is 5.0g/cm
3Be of a size of the tantalum piece of 4.0 * 3.5 * 2.3mm, by pressing method deoxidation of the present invention behind the prior art sintering, the weight ratio of tantalum piece and deoxidier adopts 1:0.005, is evacuated to 1 * 10
-3Torr also remains this vacuum degree, and temperature rises to 800 ℃ of insulations 1 hour.The metal deoxidier of removing tantalum piece remained on surface by method of the present invention with and oxide after, oxygen content in the tantalum piece after the sampling measurement deoxidation, oxygen content value as shown in the table is reduced between 2780ppm～3150ppm.Accomplish tantalum capacitor production according to existing technology again, leakage current measurement is carried out in sampling, reduces to 1.05 ~ 1.15 μ A like its leakage current value of following table.
On the basis of carrying out above-mentioned confirmatory experiment, measure make according to prior art with above-mentioned 3 confirmatory experiments in the tantalum piece oxygen content of same size, oxygen content value as shown in the table is respectively 1170～1300ppm, 1740～1850ppm and 3670～4350ppm.Measure the leakage current value that same size adopts the tantalum capacitor of prior art making, its leakage current value as shown in the table is respectively 0.38～0.45 μ A, 0.29～0.32 μ A and 2.2～2.6 μ A.
Confirmatory experiment and prior art contrast can be known; The tantalum piece that adopts the inventive method sintering is under identical testing conditions; Reduced the oxygen content of tantalum piece, the tantalum capacitor leakage current value of utilizing its manufacturing is descended significantly, created good condition for making the high-quality tantalum capacitor.
Claims (9)
1. sintering method that reduces the tantalum capacitor leakage current value; It is characterized in that; Lower and itself or oxide are prone to be placed on co-sintered in the vacuum sintering furnace with the metal of water or acid reaction as deoxidier and tantalum piece with fusing point, and vacuum degree is all the time greater than 2 * 10 in the sintering process
-3Torr.
2. a kind of sintering method that reduces the tantalum capacitor leakage current value as claimed in claim 1 is characterized in that described sintering temperature is between 700 ~ 1170 ℃.
3. a kind of sintering method that reduces the tantalum capacitor leakage current value as claimed in claim 1 is characterized in that described sintering temperature is between 900 ~ 1000 ℃.
4. a kind of sintering method that reduces the tantalum capacitor leakage current value as claimed in claim 1 is characterized in that the weight ratio of said tantalum piece and deoxidier is 1:0.001 ~ 1:0.08.
5. a kind of sintering method that reduces the tantalum capacitor leakage current value as claimed in claim 1 is characterized in that the weight ratio of tantalum piece and deoxidier is 1:0.009 ~ 1:0.06.
6. a kind of sintering method that reduces the tantalum capacitor leakage current value as claimed in claim 1 is characterized in that, the temperature retention time that reaches after the sintering temperature is 1 ~ 9 hour.
7. a kind of sintering method that reduces the tantalum capacitor leakage current value as claimed in claim 1 is characterized in that, the temperature retention time that reaches after the sintering temperature is 5 ~ 7 hours.
8. a kind of sintering method that reduces the tantalum capacitor leakage current value as claimed in claim 1 is characterized in that, described deoxidier adopts magnesium.
9. a kind of sintering method that reduces the tantalum capacitor leakage current value as claimed in claim 1 is characterized in that, accomplishes the deoxidation sintering and after vacuum state drops to room temperature, the tantalum piece is put into diluted acid immersion 30 minutes, uses deionized water rinsing again 3～4 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102369825A CN102779656A (en) | 2012-07-10 | 2012-07-10 | Sintering method for lowering leakage current value of tantalum capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102369825A CN102779656A (en) | 2012-07-10 | 2012-07-10 | Sintering method for lowering leakage current value of tantalum capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102779656A true CN102779656A (en) | 2012-11-14 |
Family
ID=47124533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102369825A Pending CN102779656A (en) | 2012-07-10 | 2012-07-10 | Sintering method for lowering leakage current value of tantalum capacitor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102779656A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112496326A (en) * | 2020-11-10 | 2021-03-16 | 中南大学 | Oxygen removing process for injection molding titanium alloy and application thereof |
| CN113077989A (en) * | 2021-03-31 | 2021-07-06 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Preparation method of anode tantalum block of low-oxygen-content solid electrolyte tantalum capacitor |
| CN115831617A (en) * | 2022-12-13 | 2023-03-21 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Method for manufacturing tantalum capacitor sintered tantalum block |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU452431A1 (en) * | 1972-03-22 | 1974-12-05 | Государственный научно-исследовательский и проектный институт редкометаллической промышленности | The mixture for the manufacture of sintered materials based on tantalum |
| CN1247576A (en) * | 1997-02-19 | 2000-03-15 | H.C.施塔克公司 | Tantalum powder, method for producing same powder and sintered anodes obtained from it |
| US20060065073A1 (en) * | 2004-09-29 | 2006-03-30 | Shekhter Leonid N | Magnesium removal from magnesium reduced metal powders |
| CN102225764A (en) * | 2011-05-25 | 2011-10-26 | 山东理工大学 | Preparation method of tantalum carbide powder |
| CN102367568A (en) * | 2011-10-20 | 2012-03-07 | 宁波江丰电子材料有限公司 | Preparation method of high-purity tantalum target material |
-
2012
- 2012-07-10 CN CN2012102369825A patent/CN102779656A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU452431A1 (en) * | 1972-03-22 | 1974-12-05 | Государственный научно-исследовательский и проектный институт редкометаллической промышленности | The mixture for the manufacture of sintered materials based on tantalum |
| CN1247576A (en) * | 1997-02-19 | 2000-03-15 | H.C.施塔克公司 | Tantalum powder, method for producing same powder and sintered anodes obtained from it |
| US20060065073A1 (en) * | 2004-09-29 | 2006-03-30 | Shekhter Leonid N | Magnesium removal from magnesium reduced metal powders |
| CN102225764A (en) * | 2011-05-25 | 2011-10-26 | 山东理工大学 | Preparation method of tantalum carbide powder |
| CN102367568A (en) * | 2011-10-20 | 2012-03-07 | 宁波江丰电子材料有限公司 | Preparation method of high-purity tantalum target material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112496326A (en) * | 2020-11-10 | 2021-03-16 | 中南大学 | Oxygen removing process for injection molding titanium alloy and application thereof |
| CN113077989A (en) * | 2021-03-31 | 2021-07-06 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Preparation method of anode tantalum block of low-oxygen-content solid electrolyte tantalum capacitor |
| CN115831617A (en) * | 2022-12-13 | 2023-03-21 | 中国振华(集团)新云电子元器件有限责任公司(国营第四三二六厂) | Method for manufacturing tantalum capacitor sintered tantalum block |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7731893B2 (en) | Method for making anodes for electrolytic capacitor with high volumetric efficiency | |
| CN104061761B (en) | The furnace drying method of lithium ion battery or battery pole piece | |
| CN101892434A (en) | Ultra-high temperature electrothermal alloy and preparation method thereof | |
| CN104313525B (en) | A kind of rolling processing method of tungsten alloy sheet material | |
| CN102779656A (en) | Sintering method for lowering leakage current value of tantalum capacitor | |
| JP2015127457A (en) | Valve metal particles and manufacturing method thereof | |
| CN105665731B (en) | A kind of tantalum powder preparation method | |
| CN115213405B (en) | Preparation method of high-pressure-resistance copper-chromium contact material | |
| CN101728540A (en) | Quick age-hardening method for grid of lead-acid accumulator | |
| CN114959356B (en) | Copper-based precise resistance alloy with high resistivity and low temperature drift and preparation method thereof | |
| CN103500658B (en) | The method reducing leakage current of high-voltage large-capacity tantalum electrolytic capacitor | |
| CN103469135B (en) | Preparation method of high-niobium TiAl intermetallic compound | |
| CN102912154B (en) | Melting process for increasing conductivity of red copper | |
| CN104404280A (en) | Preparation method for superlattice RE-Mg-Ni hydrogen storage alloy | |
| CN104250711A (en) | Casting method for flange alloy material | |
| CN102776563A (en) | Impurity removing method used for ingot furnace | |
| CN110904397B (en) | Multi-stage annealing process of high-voltage anode aluminum foil for electrolytic capacitor | |
| CN101463445B (en) | A kind of NiCoMnSn high temperature shape memory alloy and preparation method thereof | |
| CN105506340A (en) | Preparation method for anode of copper-phosphorus alloy | |
| CN107345279A (en) | A kind of preparation method of superplasticity Ni Mn Ga Ta high temperature shape memory alloy | |
| CN104294087B (en) | The preparation method of superlattice hydrogen storage alloy | |
| CN107130141B (en) | A kind of high-ductility, the preparation method of high intensity Ni-Mn-Ga-Hf memorial alloys | |
| CN100497684C (en) | Production method of calcium lead alloy | |
| JP6039868B2 (en) | Method for producing negative electrode current collector for secondary battery | |
| CN104745877A (en) | Heat treatment technology of La-Mg-Ni series A5B19 phase hydrogen storage alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20121114 |