CN105153974A - Aqueous composite binder and method for preparing aqueous positive electrode slurry therefrom - Google Patents
Aqueous composite binder and method for preparing aqueous positive electrode slurry therefrom Download PDFInfo
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- CN105153974A CN105153974A CN201510443961.4A CN201510443961A CN105153974A CN 105153974 A CN105153974 A CN 105153974A CN 201510443961 A CN201510443961 A CN 201510443961A CN 105153974 A CN105153974 A CN 105153974A
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- 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
Abstract
The invention provides an aqueous composite binder and a method for preparing aqueous positive electrode slurry therefrom. The aqueous composite binder is prepared through blending the ingredients in parts by mass: 65-70 parts of primary binder, 30-35 parts of ionic binder and 1.5 parts of flexibilizer, wherein a -COOLi functional group containing water-soluble polymer, or water-soluble lithium-containing silicate or a water-soluble binder capable of forming a complex with free Li<+> serves as the ionic binder, a long-chain water-soluble polymer with adsorption and flocculation effects serves as the flexibilizer, and a water-soluble polymer serves as the primary binder. The aqueous composite binder and the method for preparing the aqueous positive electrode slurry therefrom have the advantages that the problem that Mn is dissolved in a cycle process of spinel lithium manganate batteries can be effectively solved, and prepared batteries are more environment-friendly and are better in charging and discharging properties.
Description
Technical field
The present invention relates to materials chemistry and new energy field, be specifically related to water-based compound binding agent and preparation method thereof, use the water-based compound binding agent that obtains of the method to be applied in the preparation of based lithium-ion battery positive plate.
Background technology
Lithium ion battery, as the first march of contemporary battery industry, the main rechargeable battery being applied in portable type electronic product, power tool and electromobile etc.Domestic and external electric automobile market constantly expands, and the demand of lithium ion battery also will constantly increase.Prepare lithium ion battery and need subsidiary material binding agent, it is also the important factor affecting battery formation and over-all properties thereof.Manganese-based anode material is the lithium electricity positive electrode material studied comparatively early, have cheap, security good, overcharge resistance performance good, be easy to the advantages such as synthesis, is one of power lithium battery positive electrode material of most development prospect.
But also there is following shortcoming: one is, this type of positive electrode material mostly is semiconductor structure, and electronics, ionic conductivity are low; Two are, the decomposition of lithium salts in electrolytic solution, causes manganese to dissolve, and two of dissolve area gradually become individual event structure, and the product of electrolyte decomposition can cause polarization of electrode impedance to increase.Repeatedly embedding and the Swelling and contraction deviating to cause structure of lithium ion, even occur subsiding, cause structural symmetry to reduce, crystalline structure is converted into tetragonal system by isometric system.Due to two coexist time structure incompatible, can not well contact between electrode material particles, Li
+diffusion difficulty, polarization increases, and cause irreversible capacity loss to increase, cannot meet the larger charging and discharging currents of battery and cycle life, the conduction of lithium ion, electronics also relies on binding agent and active material junction.
Summary of the invention
The object of the present invention is to provide and a kind ofly can improve the water-based compound binding agent of spinel manganese base anode material cyclical stability and prepare aqueous positive-pole slurry methods, and its application in lithium ion battery is provided.The lithium ion battery internal resistance adopting this water-based compound binding agent obtained is little, and charge-discharge performance is excellent.
The object of the invention is to be achieved through the following technical solutions.
A kind of water-based compound binding agent, comprise with containing-COOLi functional group water-soluble polymers, water-soluble containing lithium silicates class or can with free Li
+the water-soluble binder forming complex compound is ionic binding agent; There is the long-chain water-soluble polymers of adsorption-flocculation effect for flexibility agent; Take water-soluble polymers as main binder, three's blended formation water-based compound binding agent; Its separately moiety by mass fraction be: main binder 65-70 part; Ionic binding agent 30-35 part; Flexibility agent 1.5 parts.
Further preferably, described ionic binding agent is at least one be selected from containing the water-soluble polymers of-COOLi functional group in carboxymethyl cellulose lithium, Lithium polyacrylate, polymethyl acrylic acid lithium and derivative thereof.
Further preferably, described ionic binding agent is water-soluble containing lithium silicates class, is specially lithium silicate.
Further preferably, described ionic binding agent be can with free Li
+form the water-soluble binder of complex compound, be specially polyoxyethylene.
Further preferably, described ionic binding agent is carboxymethyl cellulose lithium, and its preparation method specifically comprises: be scattered in by Xylo-Mucine in ethanol, add acid dissolve under stirring, insolubles to be had is separated out, and adds the ethanol of 90%, precipitation, filter, washing, dry carboxymethyl cellulose; Carboxymethyl cellulose is scattered in ethanol, adds lithium hydroxide solution, be stirred to carboxymethyl cellulose and all dissolve, add the ethanol of 90%, precipitation, filter, washing, dry carboxymethyl cellulose lithium, is dissolved in deionized water and forms the aqueous solution that massfraction is 2%.
Further preferably, described flexibility agent is one or more in partially hydrolyzed polyacrylamide, polyacrylamide, polyoxyethylene, polyvinylpyrrolidone and polyvinyl alcohol.
Further preferably, described flexibility agent is partially hydrolyzed polyacrylamide, and its preparation method specifically comprises: polyacrylamide is soluble in water, add lithium hydroxide, be heated to 40 ~ 90 DEG C, stir 2 ~ 8h, be cooled to room temperature, add organic solvent such as ethanol and separate out to there being solid, leave standstill, suction filtration, washing, dry, bake out temperature is 50 ~ 80 DEG C, be dissolved in deionized water, forming massfraction is the aqueous solution of 0.15%.
Further preferably, described main binder is polyvinyl alcohol, is specially and solution is heated to 50 ~ 80 DEG C, all dissolve to polyvinyl alcohol, and forming massfraction is the aqueous solution of 10%.
A kind of water-based compound binding agent as mentioned above prepares aqueous positive-pole slurry methods, comprising: take water-based compound binding agent 8 parts, conductive agent 10 parts, positive electrode material 82 parts, deionized water 200-250 part by mass fraction; By above-mentioned each component water-based compound binding agent respectively deionized water join in whipping appts dissolve obtain macromolecular solution; Conductive agent is joined in macromolecular solution, rapid stirring at least 1 hour; Add positive electrode material, stir at least 3 hours, add a small amount of ethanol froth breaking, obtain anode sizing agent.
Further preferably, described positive electrode material is aluminium doped spinel lithium manganate, and its preparation method is as follows: the first stoichiometrically anhydrous Li of accurate weighing
2cO
3, electrolysis MnO
2with γ-Al
2o
3, move in alumina crucible after then fully grinding in agate mortar, in air atmosphere, with the ramp to 800 DEG C of 10 DEG C/min, insulation 12h, namely can take out after naturally cooling to room temperature, obtain target product.
The present invention compared with prior art, beneficial effect is: the present invention adopts water-based compound binding agent to replace traditional polyvinylidene difluoride (PVDF) as after lithium ion battery binding agent, achieve the adhesive property more more superior than conventional binders, the battery simultaneously prepared has outstanding premium properties.1) functional group such as acid amides, carboxyl, hydroxyl introduced due to water-based compound binding agent has good interfacial adhesion effect, effectively ensure that the adhesive attraction of binding agent to active substance, these functional groups also can form chemical bond with the hydroxyl of active substance, conductive agent simultaneously, thus enhance the bonding force of active substance and conductive carbon, carboxyl and collector easily form complexing action and improve bonding to collector in addition, thus ensure that the fatigue resistance that battery is enough in repeated charge-discharge cycles, reduce the velocity of variation of the thickness of battery in working cycle.2) in electrocondution slurry preparation process, because water-based compound binding agent has suitable surface tension, as easy as rolling off a logly to sprawl at active material surface or collector, and on active substance, form a continuous film after the drying, to active substance, there is good adhesion characteristics, in working cycle, bonded dose of the part surface of active substance covers preferably, the surface-area exposed in the electrolytic solution greatly reduces, thus decrease the irreversible consumption of electrolytic solution at active material surface, ensure the charge-discharge performance of battery.3) what use the present invention to prepare just has less impedance, better dynamic property performance, and effectively can solve the spinel lithium manganate battery problem that Mn dissolves in working cycle, the battery more environmental protection of preparation, charge-discharge performance are better.
Accompanying drawing explanation
Fig. 1 is LiMn prepared by PVDF and water-based compound binding agent
2o
4the cycle performance of battery compares;
Fig. 2 is LiMn prepared by PVDF and water-based compound binding agent
2o
4the specific storage of battery and the relation of voltage;
Fig. 3 LiMn
2o
4the alternating-current impedance figure of battery;
Fig. 4 is LiAl prepared by PVDF and water-based compound binding agent
0.04mn
1.96o
4the cycle performance of battery compares;
Fig. 5 is LiAl prepared by PVDF and water-based compound binding agent
0.04mn
1.96o
4the specific storage of battery and the relation of voltage;
Fig. 6 LiAl
0.04mn
1.96o
4the alternating-current impedance figure of battery;
LiAl prepared by Fig. 7 two kinds of binding agents
0.04mn
1.96o
4scanning electron microscope (SEM) photograph (a) (b) (c) of positive plate is PVDF/LiAl
0.04mn
1.96o
4pole piece is respectively at the scanning electron microscope (SEM) photograph of 1000,10000,50000 times; D () (e) (f) is WSCB/LiAl
0.04mn
1.96o
4pole piece is respectively at the scanning electron microscope (SEM) photograph of 1000,10000,50000 times.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
In the present invention, a kind of water-based compound binding agent that can improve spinel manganese base anode material cyclical stability, it be with containing-COOLi functional group water-soluble polymers, water-soluble containing lithium silicates class or can with free Li
+the water-soluble binder forming complex compound is ionic binding agent; There is the long-chain water-soluble polymers of adsorption-flocculation effect for flexibility agent; Take water-soluble polymers as main binder, three's blended formation water-based compound binding agent.
Below, by specific embodiment in detail implementation result of the present invention is described in detail.
The preparation of [embodiment 1] positive pole
This water-based compound binding agent is adopted to comprise following component: in table 1
| Water-soluble polymers | Polyvinyl alcohol | 65-70 part |
| Ionic binding agent | Carboxymethyl cellulose lithium | 30-35 part |
| Flexibility agent | Partially hydrolyzed polyacrylamide | 1.5 part |
Table 1
The aqueous positive-pole slurry adopting this water-based compound binding agent to prepare comprises following component: in table 2
| Water-based compound binding agent | 8 parts |
| Conductive agent acetylene black | 10 parts |
| Positive electrode material | 82 parts |
| Deionized water | 200-250 part |
Table 2
In above water-based compound binding agent, partially hydrolyzed polyacrylamide is prepared by such method: polyacrylamide is soluble in water, adds lithium hydroxide, be heated to 40 ~ 90 DEG C, stir 2 ~ 8h, be cooled to room temperature, add organic solvent such as ethanol to separate out to there being solid, leave standstill, suction filtration, washing, dry, bake out temperature is 50 ~ 80 DEG C, is dissolved in deionized water, and forming massfraction is the aqueous solution of 0.15%.
Polyvinyl alcohol dissolution adopts such preparation method in solution, solution is heated to 50 ~ 80 DEG C, all dissolves to polyvinyl alcohol, and forming massfraction is the aqueous solution of 10%.
Carboxymethyl cellulose lithium adopts such preparation method, is scattered in by Xylo-Mucine in ethanol, stirs lower acid adding (hydrochloric acid or sulfuric acid) and dissolves, insolubles to be had is separated out, add the ethanol of 90%, precipitation, filter, washing, dry carboxymethyl cellulose; Carboxymethyl cellulose is scattered in ethanol, adds lithium hydroxide solution, be stirred to carboxymethyl cellulose and all dissolve, add the ethanol of 90%, precipitation, filter, washing, dry carboxymethyl cellulose lithium, is dissolved in deionized water and forms the aqueous solution that massfraction is 2%.
Partially hydrolyzed polyacrylamide, polyvinyl alcohol, carboxymethyl cellulose lithium form water-based compound binding agent according to above-mentioned component blend, particularly, by main binder, ionic binding agent, flexibility agent respectively deionized water join in whipping appts and dissolve, obtain the solution of each component, these three kinds of solution are obtained macromolecular solution by formula ratio is blended; The conductive agent of formula ratio is joined in macromolecular solution, rapid stirring at least 1 hour; Add the active substance of formula ratio, stir at least 3 hours, add a small amount of ethanol froth breaking, obtain anode sizing agent; Anode sizing agent is coated on equably on collector one side aluminium foil, naturally dries, then oven dry obtains lithium ion cell positive.
Relative to water-based compound binding agent, not containing solvent, wherein the weight percent of partially hydrolyzed polyacrylamide is 0.15%, polyvinyl alcohol: carboxymethyl cellulose lithium is 2:1.
Described positive electrode material is aluminium doped spinel lithium manganate, and its preparation method is as follows:
Doped spinel type lithium manganate LiAl
0.04mn
1.96o
4prepared by high temperature solid-state method, main method and condition as described below: the first stoichiometrically anhydrous Li of accurate weighing
2cO
3, electrolysis MnO
2with γ-Al
2o
3, move in alumina crucible after then fully grinding in agate mortar, in air atmosphere, with the ramp to 800 DEG C of 10 DEG C/min, insulation 12h, namely can take out after naturally cooling to room temperature, obtain target product.
Lithium manganate having spinel structure LiMn
2o
4preparation method identical with aforesaid method, difference is the stoichiometrically anhydrous Li of accurate weighing
2cO
3with electrolysis MnO
2.
(1) coating process of anode sizing agent
With the slurry prepared above, be coated with scraper, be that the one side aluminium foil of 20um is collector with thickness, coating thickness is 400um, obtains positive plate after naturally drying.
(2) battery assembling
Above-mentioned dry after positive plate, be cut into the sequin that diameter is 14mm, be placed in 80 DEG C, baking oven, bake 8h, drier 12h at 120 DEG C, vacuum, weigh, with lithium sheet for negative plate, in glove box, be assembled into button cell, sealing, carries out electric performance test.
(3) battery testing
The battery sealed is placed in the blue electrical testing system of LAND, leaves standstill 3h, first charge to required voltage, then constant voltage charge 0.5h, finally with required multiplying power discharging to required voltage.
[embodiment 2] method steps is the same, changes LiMn into unlike active substance
2o
4, the ratio of binding agent, conductive agent, active substance three is 7:10:83.
[embodiment 3] method steps is the same, is made up of partially hydrolyzed polyacrylamide, polyvinyl alcohol, lithium silicate aqueous solution unlike compound binding agent, and active substance is LiMn
2o
4, the ratio of binding agent, conductive agent, active substance three is 7:10:83.
[embodiment 4] method steps is the same, is made up of polyoxyethylene, polyvinyl alcohol, lithium silicate aqueous solution unlike compound binding agent, and active substance is LiMn
2o
4, the ratio of binding agent, conductive agent, active substance three is 7:10:83.
[embodiment 5] method steps is the same, is made up of polyoxyethylene, polyvinylpyrrolidone, lithium silicate aqueous solution unlike compound binding agent, and active substance is LiMn
2o
4, the ratio of binding agent, conductive agent, active substance three is 7:10:83.
[embodiment 6] method steps is the same, is made up of polyacrylamide, polyoxyethylene glycol, lithium silicate aqueous solution unlike compound binding agent, and active substance is LiMn
2o
4, the ratio of binding agent, conductive agent, active substance three is 7:10:83.
[embodiment 7] method steps is the same, is made up of polyacrylamide, polyvinyl alcohol, carboxymethyl cellulose lithium unlike compound binding agent, and active substance is LiMn
2o
4, the ratio of binding agent, conductive agent, active substance three is 7:10:83.
[embodiment 8] method steps is the same, is made up of polyvinyl alcohol, cm-chitosan, lithium silicate aqueous solution unlike compound binding agent, and active substance is LiMn
2o
4, the ratio of binding agent, conductive agent, active substance three is 7:10:83.
[embodiment 9] method steps, with embodiment 3,4,5,6,7,8, is LiAl unlike active substance
0.04mn
1.96o
4, the ratio of binding agent, conductive agent, active substance three is 8:10:82.
Comparative example: respectively with LiMn
2o
4, LiAl
0.04mn
1.96o
4for positive electrode material, polyvinylidene difluoride (PVDF) (PVDF) be binding agent, N-Methyl pyrrolidone (NMP) obtains positive plate for solvent, positive plate consists of: positive electrode material 80 parts, acetylene black 10 parts, PVDF10 part, NMP100 part.Obtain battery by above-mentioned steps, difference is, when PVDF is dissolved in NMP, need be heated to 45 DEG C, and heat-up time is 3-5h; It is dry that slurry has been coated with the rear baking oven that is directly placed in.
Tested by Fig. 1-7 and show, compared with PVDF system, when making use compound system, the specific discharge capacity of electrode is significantly improved, and the distance between charging and discharging curve is less, and charge transfer resistance is lower, polarizes less.One is because battery is in circulation first, part Li
+take part in the generation of solid-liquid interface zone of oxidation SEI film, the non-reversibility of battery can be caused to strengthen, ionic binding agent in water-based compound system can provide lithium ion, and reduce the non-reversibility first of battery, therefore the first discharge specific capacity of water-based compound system is higher.Two is because conductive agent and binder phase mutual effect are wrapped on positive electrode material particle equably, define good conductive network, and with PVDF as binding agent time, conductive agent is then between positive electrode material particle, and there is serious agglomeration, part positive electrode material does not contact with conductive agent, binding agent, and thus electroconductibility is poor.Three is because water-based compound system improves interface property between electrode and ionogen, need lithium ion during active substance generation reduction reaction, and this part lithium ion can provide by close to the lithium ion in the Ionomer in the water-based compound binding agent of reactive center.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a water-based compound binding agent, is characterized in that, comprise with containing-COOLi functional group water-soluble polymers, water-soluble containing lithium silicates class or can with free Li
+the water-soluble binder forming complex compound is ionic binding agent; There is the long-chain water-soluble polymers of adsorption-flocculation effect for flexibility agent; Take water-soluble polymers as main binder, three's blended formation water-based compound binding agent; Its separately moiety by mass fraction be: main binder 65-70 part; Ionic binding agent 30-35 part; Flexibility agent 1.5 parts.
2. water-based compound binding agent as claimed in claim 1, it is characterized in that, described ionic binding agent is at least one be selected from containing the water-soluble polymers of-COOLi functional group in carboxymethyl cellulose lithium, Lithium polyacrylate, polymethyl acrylic acid lithium and derivative thereof.
3. water-based compound binding agent as claimed in claim 1, is characterized in that, described ionic binding agent is water-soluble containing lithium silicates class, is specially lithium silicate.
4. water-based compound binding agent as claimed in claim 1, is characterized in that, described ionic binding agent be can with free Li
+form the water-soluble binder of complex compound, be specially polyoxyethylene.
5. water-based compound binding agent as claimed in claim 2, it is characterized in that, described ionic binding agent is carboxymethyl cellulose lithium, its preparation method specifically comprises: be scattered in by Xylo-Mucine in ethanol, add acid dissolve under stirring, insolubles to be had is separated out, and adds the ethanol of 90%, precipitation, filter, washing, dry carboxymethyl cellulose; Carboxymethyl cellulose is scattered in ethanol, adds lithium hydroxide solution, be stirred to carboxymethyl cellulose and all dissolve, add the ethanol of 90%, precipitation, filter, washing, dry carboxymethyl cellulose lithium, is dissolved in deionized water and forms the aqueous solution that massfraction is 2%.
6. water-based compound binding agent as claimed in claim 1, it is characterized in that, described flexibility agent is one or more in partially hydrolyzed polyacrylamide, polyacrylamide, polyoxyethylene, polyvinylpyrrolidone and polyvinyl alcohol.
7. water-based compound binding agent as claimed in claim 6, it is characterized in that, described flexibility agent is partially hydrolyzed polyacrylamide, its preparation method specifically comprises: polyacrylamide is soluble in water, adds lithium hydroxide, is heated to 40 ~ 90 DEG C, stir 2 ~ 8h, be cooled to room temperature, add organic solvent such as ethanol and separate out to there being solid, leave standstill, suction filtration, washing, dry, bake out temperature is 50 ~ 80 DEG C, is dissolved in deionized water, and forming massfraction is the aqueous solution of 0.15%.
8. water-based compound binding agent as claimed in claim 1, it is characterized in that, described main binder is polyvinyl alcohol, is specially and solution is heated to 50 ~ 80 DEG C, all dissolve to polyvinyl alcohol, and forming massfraction is the aqueous solution of 10%.
9. preparing an aqueous positive-pole slurry methods as weighed water-based compound binding agent as described in 1, it is characterized in that, comprise: take water-based compound binding agent 8 parts, conductive agent 10 parts, positive electrode material 82 parts, deionized water 200-250 part by mass fraction; By above-mentioned each component water-based compound binding agent respectively deionized water join in whipping appts dissolve obtain macromolecular solution; Conductive agent is joined in macromolecular solution, rapid stirring at least 1 hour; Add positive electrode material, stir at least 3 hours, add a small amount of ethanol froth breaking, obtain anode sizing agent.
10. water-based compound binding agent as claimed in claim 9 prepares aqueous positive-pole slurry methods, and it is characterized in that, described positive electrode material is aluminium doped spinel lithium manganate, and its preparation method is as follows: the first stoichiometrically anhydrous Li of accurate weighing
2cO
3, electrolysis MnO
2with γ-Al
2o
3, move in alumina crucible after then fully grinding in agate mortar, in air atmosphere, with the ramp to 800 DEG C of 10 DEG C/min, insulation 12h, namely can take out after naturally cooling to room temperature, obtain target product.
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| CN109309232A (en) * | 2018-09-13 | 2019-02-05 | 深圳市电科电源股份有限公司 | A kind of preparation method of lithium ion battery with high energy density |
| CN111668483B (en) * | 2019-03-09 | 2022-04-15 | 江苏道赢科技有限公司 | Battery electrode binder and preparation method thereof |
| CN111668483A (en) * | 2019-03-09 | 2020-09-15 | 江苏道赢科技有限公司 | Battery electrode binder and preparation method thereof |
| CN110911644A (en) * | 2019-10-30 | 2020-03-24 | 深圳市卓能新能源股份有限公司 | Lithium ion positive coating and lithium ion battery |
| CN112968177B (en) * | 2021-03-01 | 2022-02-22 | 广州鹏辉能源科技股份有限公司 | Water-based anode slurry composition, water-based anode slurry, preparation method of water-based anode slurry, anode plate, lithium ion battery and power utilization equipment |
| CN112968177A (en) * | 2021-03-01 | 2021-06-15 | 广州鹏辉能源科技股份有限公司 | Water-based anode slurry composition, water-based anode slurry, preparation method of water-based anode slurry, anode plate, lithium ion battery and power utilization equipment |
| CN113725438A (en) * | 2021-09-02 | 2021-11-30 | 广州市乐基智能科技有限公司 | Water-based composite binder for solid-state lithium battery and application thereof |
| CN113871622A (en) * | 2021-09-15 | 2021-12-31 | 惠州赣锋锂电科技有限公司 | Binder for lithium ion battery cathode, cathode slurry using same and preparation method thereof |
| CN114335422A (en) * | 2021-12-30 | 2022-04-12 | 珠海冠宇电池股份有限公司 | Negative plate and lithium ion battery comprising same |
| CN115425226A (en) * | 2022-08-18 | 2022-12-02 | 楚能新能源股份有限公司 | Ternary material flexible positive electrode and preparation method thereof |
| CN115425226B (en) * | 2022-08-18 | 2023-04-14 | 楚能新能源股份有限公司 | Ternary material flexible positive electrode and preparation method thereof |
| CN117334917A (en) * | 2023-12-01 | 2024-01-02 | 宁德时代新能源科技股份有限公司 | Secondary battery and electricity utilization device |
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Denomination of invention: The invention relates to a water-based composite binder and a method for preparing water-based positive paste Effective date of registration: 20201229 Granted publication date: 20190115 Pledgee: Shenzhen hi tech investment small loan Co.,Ltd. Pledgor: Shenzhen Tenglongyuan Industrial Co.,Ltd. Registration number: Y2020980010201 |