CN109786716A - A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode - Google Patents
A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode Download PDFInfo
- Publication number
- CN109786716A CN109786716A CN201910089388.XA CN201910089388A CN109786716A CN 109786716 A CN109786716 A CN 109786716A CN 201910089388 A CN201910089388 A CN 201910089388A CN 109786716 A CN109786716 A CN 109786716A
- Authority
- CN
- China
- Prior art keywords
- carbon cloth
- composite material
- sodium
- ion battery
- preparation
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inert Electrodes (AREA)
Abstract
A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode, and the present invention is using water and glycerine as mixed solvent, with SnCl2·2H2O uses simple hydro-thermal method to be prepared for partial size as 0.5~1 μm of Sn/ carbon cloth composite material, is assembled into sodium-ion battery using it as negative electrode material as tin source, the Na generated due to metal Sn and sodium ion generation alloying reaction15Sn4Theoretical capacity with higher, carbon cloth replaces conventional metals collector to have biggish specific surface area as matrix simultaneously, by preparing self-supporting electrode, the addition of bonding agent and conductive agent is not necessarily to during composite electrode material, active material accounting is big, simultaneously because the presence of carbon cloth can also be improved the electric conductivity of negative electrode material.Therefore Sn/ carbon cloth composite material shows preferable chemical property.In addition, preparation method simple process of the present invention, the carbon source used is low in cost, reaction temperature is low, it is repeated it is high, the period is short, low energy consumption, save production cost.
Description
Technical field
The invention belongs to sodium-ion battery alloy type negative material technical field, in particular to a kind of Sn/ carbon cloth composite
Material does the preparation method of sodium-ion battery cathode.
Background technique
With the development of bending foldable electronic, it is current research that developing, which has the flexible battery of high-energy density,
One of hot spot.Exploitation flexible battery focuses on developing with high-energy density electrode material flexible.Currently, sodium ion is electric
Pond cathode mainly uses carbon graphite negative electrode material, although carbon graphite negative electrode material has preferable cyclical stability,
Theoretical capacity only has 250~300mAh/g, and relatively low theoretical capacity limits its application as sodium-ion battery cathode
Prospect.In the research to negative electrode material, it is carbon graphite that theoretical capacity of the simple substance Sn in sodium-ion battery, which reaches 847mAh/g,
Change more than twice of materials theory capacity, which results in the extensive concerns of battery material circle.
However, simple substance Sn can generate biggish volume expansion during sodium ion deintercalation, this be will lead in charge and discharge
The powder of detached of material in the process reduces the cycle performance of battery, greatly affected the practical application of this kind of material.And incite somebody to action
Negative electrode material nanosizing, with carbon material is compound and preparation self-supporting electrode etc. can a degree of alleviation volume expansion bring
The problem of.
Summary of the invention
The purpose of the present invention is to provide the preparation methods that a kind of Sn/ carbon cloth composite material does sodium-ion battery cathode, should
Sn/ carbon cloth composite material prepared by method has flexible folding compared to traditional electrode, and assembling is simple, excellent without collector etc.
Point, simultaneously because active material accounting is big, it is good that carbon cloth does matrix conductivity, large specific surface area, so its chemical property
It is very excellent.
To achieve the goals above, the technical solution adopted by the present invention is that:
1) carbon cloth of (2~4) × (2~4) cm is placed in 0.5~2h of immersion treatment in nitric acid solution；
2) by the SnCl of 0.63~1.52g2·2H2O is dissolved in 20~50mL deionized water and the mixing of 10~25ml glycerine is molten
Solution A 1 is stirred evenly to obtain in agent, and 5~20ml hydrazine hydrate is added into solution A 1, is then ultrasonically treated, obtains solution A 2；
3) solution A 2 and the carbon cloth that has pre-processed are transferred to after polytetrafluoroethylene (PTFE) water heating kettle together by the polytetrafluoroethyl-ne
Alkene water heating kettle is placed in homogeneous reactor in 165~185 DEG C of hydro-thermal reactions, and cooled to room temperature, then takes after reaction
Carbon cloth out；
4) carbon cloth for obtaining step 3) is put into beaker, is cleaned respectively with ethyl alcohol and deionized water, and baking oven is then placed in
Interior drying, cooled to room temperature obtain Sn/ carbon cloth composite material.
Step 1) the carbon cloth is hydrophily carbon cloth.
Step 1) the carbon cloth is respectively cleaned by ultrasonic 3~6h twice in ethyl alcohol and deionized water before impregnating.
Step 1) the nitric acid solution concentration is 0.5~1mol/L.
For the ultrasonic power that the step 2) ultrasonic treatment uses for 50~100W, the time is 5~20min.
The compactedness of the step 3) water heating kettle is 40~60%.
Step 3) the hydro-thermal reaction time be 6~for 24 hours.
Step 4) the ethyl alcohol and deionized water are respectively washed 3h.
Step 4) the oven drying temperature is 60 DEG C, and drying time is 6~12h.
Beneficial effects of the present invention:
The present invention is using water and glycerine as mixed solvent, with SnCl2·2H2O is as tin source, using simple hydro-thermal legal system
The Sn/ carbon cloth composite material for being 0.5~1 μm for partial size, is assembled into sodium-ion battery using it as negative electrode material, due to metal
The Na that alloying reaction generates occurs for Sn and sodium ion15Sn4Theoretical capacity with higher, while carbon cloth replaces conventional metals collection
Fluid has biggish specific surface area as matrix, by preparing self-supporting electrode, is not necessarily to during composite electrode material viscous
Agent and the addition of conductive agent are connect, active material accounting is big, simultaneously because the presence of carbon cloth can also be improved the conduction of negative electrode material
Property.Therefore Sn/ carbon cloth composite material shows preferable chemical property.In addition, preparation method simple process of the present invention, makes
Carbon source is low in cost, reaction temperature is low, it is repeated it is high, the period is short, low energy consumption, saves production cost, be suitble to extensive raw
The needs of preparation are produced, and there is significant scientific meaning in sodium-ion battery application aspect.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) map of Sn/ carbon cloth composite material prepared by the embodiment of the present invention 2.
Fig. 2 is scanning electron microscope (SEM) photo of Sn/ carbon cloth composite material prepared by the embodiment of the present invention 2.
Fig. 3 is the cycle performance figure of Sn/ carbon cloth composite material prepared by the embodiment of the present invention 2.
Specific embodiment
Invention is further described in detail with reference to the accompanying drawings and embodiments.
Embodiment 1:
1) the hydrophily carbon cloth of 3 × 3cm is respectively cleaned by ultrasonic 4h twice in ethyl alcohol and deionized water, then sets carbon cloth
Immersion treatment 0.5h, performs etching carbon cloth surfaces in the nitric acid solution of 0.8mol/L, subtracts surface-active carbon atom number
It is few, increase surface-active functional group；
2) by the SnCl of 0.85g2·2H2O is dissolved in 20mL deionized water and 20ml glycerine in the mixed solvent stirs evenly
5ml hydrazine hydrate is added into solution A 1 for solution A 1, is then ultrasonically treated 5min using 100W, obtains solution A 2；
3) solution A 2 and the carbon cloth pre-processed are transferred to together in polytetrafluoroethylene (PTFE) water heating kettle, control compactedness is
40%, then the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reactor (Yantai Ke Li Chemical Equipment Co., Ltd.,
KLJX-8A) for 24 hours in 165 DEG C of hydro-thermal reactions, cooled to room temperature, then takes out carbon cloth after reaction；
4) carbon cloth for obtaining step 3) is put into beaker, cleans 3h with ethyl alcohol and deionized water respectively, is then placed in baking
In 60 DEG C of dry 12h in case, cooled to room temperature obtains Sn/ carbon cloth composite material.
Embodiment 2:
1) the hydrophily carbon cloth of 3 × 3cm is respectively cleaned by ultrasonic 5h twice in ethyl alcohol and deionized water, then sets carbon cloth
Immersion treatment 2h, performs etching carbon cloth surfaces in the nitric acid solution of 0.5mol/L, reduces surface-active carbon atom number,
Increase surface-active functional group；
2) by the SnCl of 0.63g2·2H2O is dissolved in 50mL deionized water and 10ml glycerine in the mixed solvent stirs evenly
10ml hydrazine hydrate is added into solution A 1 for solution A 1, is then ultrasonically treated 5min using 100W, obtains solution A 2；
3) solution A 2 and the carbon cloth pre-processed are transferred to together in polytetrafluoroethylene (PTFE) water heating kettle, control compactedness is
60%, then the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reactor (Yantai Ke Li Chemical Equipment Co., Ltd.,
KLJX-8A) for 24 hours in 180 DEG C of hydro-thermal reactions, cooled to room temperature, then takes out carbon cloth after reaction；
4) carbon cloth for obtaining step 3) is put into beaker, cleans 3h with ethyl alcohol and deionized water respectively, is then placed in baking
In 60 DEG C of dry 12h in case, cooled to room temperature obtains Sn/ carbon cloth composite material.
As shown in Figure 1, sample (Sn/ carbon cloth composite material) is analyzed with Rigaku D/max2000PCX- x ray diffractometer x,
It was found that sample is consistent with the C-structure that the Sn and PDF card number that PDF card number is 65-5224 is 22-1069；
As shown in Fig. 2, by the field emission scanning electron microscope (FESEM) of sample FEI Co., U.S. S-4800 type
It is observed, it can be seen that the solid spherical particle that prepared Sn/ carbon cloth composite material is 0.5~1 μm of partial size.
As shown in figure 3, testing its cycle performance using BTS battery charging and discharging tester, it can be seen that prepared Sn/ carbon
Cloth negative electrode material has recycled 500 circles under the current density of 1A/g, and its specific capacity is basicly stable is maintained at 500mAh/g.
Embodiment 3:
1) the hydrophily carbon cloth of 3 × 3cm is respectively cleaned by ultrasonic 6h twice in ethyl alcohol and deionized water, then sets carbon cloth
Immersion treatment 2h, performs etching carbon cloth surfaces in the nitric acid solution of 0.6mol/L, reduces surface-active carbon atom number,
Increase surface-active functional group；
2) by the SnCl of 1.52g2·2H2O is dissolved in 20mL deionized water and 25ml glycerine in the mixed solvent stirs evenly
20ml hydrazine hydrate is added into solution A 1 for solution A 1, is then ultrasonically treated 20min using 100W, obtains solution A 2；
3) solution A 2 and the carbon cloth pre-processed are transferred to together in polytetrafluoroethylene (PTFE) water heating kettle, control compactedness is
60%, then the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reactor (Yantai Ke Li Chemical Equipment Co., Ltd.,
KLJX-8A) in 185 DEG C of hydro-thermal reaction 10h, cooled to room temperature, then takes out carbon cloth after reaction；
4) carbon cloth for obtaining step 3) is put into beaker, cleans 3h with ethyl alcohol and deionized water respectively, is then placed in baking
In 60 DEG C of dry 12h in case, cooled to room temperature obtains Sn/ carbon cloth composite material.
Embodiment 4:
1) the hydrophily carbon cloth of 4 × 4cm is respectively cleaned by ultrasonic 3h twice in ethyl alcohol and deionized water, then sets carbon cloth
Immersion treatment 1h, performs etching carbon cloth surfaces in the nitric acid solution of 1mol/L, reduces surface-active carbon atom number, increases
Add surface-active functional group；
2) by the SnCl of 1.12g2·2H2O is dissolved in 35mL deionized water and 15ml glycerine in the mixed solvent stirs evenly
10ml hydrazine hydrate is added into solution A 1 for solution A 1, is then ultrasonically treated 10min using 100W, obtains solution A 2；
3) solution A 2 and the carbon cloth pre-processed are transferred to together in polytetrafluoroethylene (PTFE) water heating kettle, control compactedness is
50%, then the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reactor (Yantai Ke Li Chemical Equipment Co., Ltd.,
KLJX-8A) in 175 DEG C of hydro-thermal reaction 6h, cooled to room temperature, then takes out carbon cloth after reaction；
4) carbon cloth for obtaining step 3) is put into beaker, cleans 3h with ethyl alcohol and deionized water respectively, is then placed in baking
In 60 DEG C of dry 6h in case, cooled to room temperature obtains Sn/ carbon cloth composite material.
Embodiment 5:
1) the hydrophily carbon cloth of 2 × 2cm is respectively cleaned by ultrasonic 4h twice in ethyl alcohol and deionized water, then sets carbon cloth
Immersion treatment 2h, performs etching carbon cloth surfaces in the nitric acid solution of 0.7mol/L, reduces surface-active carbon atom number,
Increase surface-active functional group；
2) by the SnCl of 1.52g2·2H2O is dissolved in 40mL deionized water and 10ml glycerine in the mixed solvent stirs evenly
20ml hydrazine hydrate is added into solution A 1 for solution A 1, is then ultrasonically treated 15min using 100W, obtains solution A 2；
3) solution A 2 and the carbon cloth pre-processed are transferred to together in polytetrafluoroethylene (PTFE) water heating kettle, control compactedness is
50%, then the polytetrafluoroethylene (PTFE) water heating kettle is placed in homogeneous reactor (Yantai Ke Li Chemical Equipment Co., Ltd.,
KLJX-8A) in 180 DEG C of hydro-thermal reaction 20h, cooled to room temperature, then takes out carbon cloth after reaction；
4) carbon cloth for obtaining step 3) is put into beaker, cleans 3h with ethyl alcohol and deionized water respectively, is then placed in baking
In 60 DEG C of dry 9h in case, cooled to room temperature obtains Sn/ carbon cloth composite material.
Claims (9)
1. the preparation method that a kind of Sn/ carbon cloth composite material does sodium-ion battery cathode, it is characterised in that include the following steps；
1) carbon cloth of (2~4) × (2~4) cm is placed in 0.5~2h of immersion treatment in nitric acid solution；
2) by the SnCl of 0.63~1.52g2·2H2O is dissolved in 20~50mL deionized water and 10~25ml glycerine in the mixed solvent
Solution A 1 is stirred evenly to obtain, 5~20ml hydrazine hydrate is added into solution A 1, is then ultrasonically treated, obtains solution A 2；
3) solution A 2 and the carbon cloth that has pre-processed are transferred to after polytetrafluoroethylene (PTFE) water heating kettle together by the polytetrafluoroethylene (PTFE) water
Hot kettle is placed in homogeneous reactor in 165~185 DEG C of hydro-thermal reactions, and cooled to room temperature, then takes out carbon after reaction
Cloth；
4) carbon cloth for obtaining step 3) is put into beaker, is cleaned respectively with ethyl alcohol and deionized water, is then placed in baking oven and is done
Dry, cooled to room temperature obtains Sn/ carbon cloth composite material.
2. Sn/ carbon cloth composite material according to claim 1 does the preparation method of sodium-ion battery cathode, feature exists
In: the step 1) carbon cloth is hydrophily carbon cloth.
3. Sn/ carbon cloth composite material according to claim 1 does the preparation method of sodium-ion battery cathode, feature exists
In: respectively it is cleaned by ultrasonic 3~6h twice in ethyl alcohol and deionized water before step 1) the carbon cloth immersion.
4. Sn/ carbon cloth composite material according to claim 1 does the preparation method of sodium-ion battery cathode, feature exists
In: step 1) the nitric acid solution concentration is 0.5~1mol/L.
5. Sn/ carbon cloth composite material according to claim 1 does the preparation method of sodium-ion battery cathode, feature exists
In: for the ultrasonic power that the step 2) ultrasonic treatment uses for 50~100W, the time is 5~20min.
6. Sn/ carbon cloth composite material according to claim 1 does the preparation method of sodium-ion battery cathode, feature exists
In: the compactedness of the step 3) water heating kettle is 40~60%.
7. Sn/ carbon cloth composite material according to claim 1 does the preparation method of sodium-ion battery cathode, feature exists
In: the step 3) the hydro-thermal reaction time be 6~for 24 hours.
8. Sn/ carbon cloth composite material according to claim 1 does the preparation method of sodium-ion battery cathode, feature exists
In: the step 4) ethyl alcohol and deionized water are respectively washed 3h.
9. Sn/ carbon cloth composite material according to claim 1 does the preparation method of sodium-ion battery cathode, feature exists
In: the step 4) oven drying temperature is 60 DEG C, and drying time is 6~12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910089388.XA CN109786716A (en) | 2019-01-30 | 2019-01-30 | A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910089388.XA CN109786716A (en) | 2019-01-30 | 2019-01-30 | A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109786716A true CN109786716A (en) | 2019-05-21 |
Family
ID=66502838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910089388.XA Pending CN109786716A (en) | 2019-01-30 | 2019-01-30 | A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109786716A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110277550A (en) * | 2019-06-24 | 2019-09-24 | 陕西科技大学 | A kind of different valence state and crystal form sb oxide/carbon cloth make the preparation method of flexible anode material of lithium-ion battery |
| CN110299512A (en) * | 2019-06-25 | 2019-10-01 | 西安交通大学 | A kind of preparation method of the lithium metal battery cathode of carbon/tin multiple base support |
| CN111004934A (en) * | 2019-12-19 | 2020-04-14 | 西南科技大学 | Method for extracting uranium by using coupling device of wind power generation and uranium extraction from seawater |
| CN113097486A (en) * | 2021-04-01 | 2021-07-09 | 陕西科技大学 | SnSe quantum dot/CFF compound and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017010802A (en) * | 2015-06-23 | 2017-01-12 | 住友電気工業株式会社 | Sodium ion secondary battery |
-
2019
- 2019-01-30 CN CN201910089388.XA patent/CN109786716A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017010802A (en) * | 2015-06-23 | 2017-01-12 | 住友電気工業株式会社 | Sodium ion secondary battery |
Non-Patent Citations (2)
| Title |
|---|
| YIHANG LIU等: ""SnO2 coated carbon cloth with surface modification as Na-ion battery anode"", 《NANO ENERGY》 * |
| 肖尧 等: ""球形Sn-SnSb合金纳米粒子制备及其储锂性能"", 《电化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110277550A (en) * | 2019-06-24 | 2019-09-24 | 陕西科技大学 | A kind of different valence state and crystal form sb oxide/carbon cloth make the preparation method of flexible anode material of lithium-ion battery |
| CN110299512A (en) * | 2019-06-25 | 2019-10-01 | 西安交通大学 | A kind of preparation method of the lithium metal battery cathode of carbon/tin multiple base support |
| CN111004934A (en) * | 2019-12-19 | 2020-04-14 | 西南科技大学 | Method for extracting uranium by using coupling device of wind power generation and uranium extraction from seawater |
| CN111004934B (en) * | 2019-12-19 | 2021-03-23 | 西南科技大学 | Method for extracting uranium by using coupling device of wind power generation and uranium extraction from seawater |
| CN113097486A (en) * | 2021-04-01 | 2021-07-09 | 陕西科技大学 | SnSe quantum dot/CFF compound and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109786716A (en) | A kind of Sn/ carbon cloth composite material does the preparation method of sodium-ion battery cathode | |
| CN108550821B (en) | Preparation method of core-shell structure nickel phosphide/carbon microspheres based on Ni-MOF | |
| CN102013470B (en) | Foam metal matrix oxide electrode used in lithium-ion battery cathode and preparation method thereof | |
| CN107732180B (en) | A kind of preparation method for water system sodium-ion battery anode composite material | |
| CN108695495B (en) | Reduced graphene oxide modified antimony trisulfide battery cathode material | |
| CN106848386B (en) | A kind of sodium-ion battery cathode nest like Sb2Se3The preparation method of electrode material | |
| CN104852028A (en) | Lithium titanate/graphene composite cathode material for lithium ion battery | |
| CN109742353A (en) | A kind of SnSe quantum dot/r-GO compound and its preparation method and application | |
| CN109817918A (en) | Sulfur doping MXene composite material and preparation method and application | |
| CN108511725A (en) | Antimony oxide/carbon nano tube/graphene nanocomposite and its preparation and application | |
| CN101071853A (en) | Nano lithium titanate for Negative electrode material of cell or electrochemical vessel, and its and titanium dioxide composite preparing method | |
| CN109713291A (en) | Sodium-ion battery cathode carbon cloth/tin flexible electrode material preparation method | |
| CN111370675B (en) | Carbon nanosheet sodium ion battery cathode material inlaid with metal phosphide and preparation method thereof | |
| CN110797512A (en) | Silicon-carbon negative electrode material, lithium ion battery negative electrode and lithium ion battery | |
| CN103008653B (en) | Carbon coated lead composite material and preparation method thereof | |
| CN113401948B (en) | Negative electrode Fe of lithium ion battery 7 S 8 /Fe 2 O 3 Composite material, preparation method and application | |
| CN105742561A (en) | Preparation method and application of flexible self-supporting composite electrode | |
| CN109817934A (en) | A kind of hydro-thermal calcination method preparation carbon coating Sn/SnO2The method of/carbon cloth negative electrode material | |
| CN106410153A (en) | Titanium nitride-cladded nickel titanate composite material as well as preparation method and application thereof | |
| CN109301186B (en) | Coated porous ternary cathode material and preparation method thereof | |
| CN110371934A (en) | A kind of preparation method of carbon-based sulphur selenizing molybdenum composite material | |
| CN107275639A (en) | CoP/C classifying nano lines of nano particle assembling and its preparation method and application | |
| CN107464938A (en) | A kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and the application in lithium-air battery | |
| CN108899537A (en) | A kind of lithium ion battery LiNixCoyMnl-x-yO2The preparation method of positive electrode | |
| CN106887572A (en) | A kind of antimony carbon composite and its preparation method and application |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190521 |
|
| WD01 | Invention patent application deemed withdrawn after publication |