CN112086631A - Preparation method of Sn-based negative electrode plate of lithium ion battery - Google Patents
Preparation method of Sn-based negative electrode plate of lithium ion battery Download PDFInfo
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- CN112086631A CN112086631A CN202010986688.0A CN202010986688A CN112086631A CN 112086631 A CN112086631 A CN 112086631A CN 202010986688 A CN202010986688 A CN 202010986688A CN 112086631 A CN112086631 A CN 112086631A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 98
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 239000011258 core-shell material Substances 0.000 claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011889 copper foil Substances 0.000 claims abstract description 17
- 239000011268 mixed slurry Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000006258 conductive agent Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 6
- 239000004626 polylactic acid Substances 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 241000784732 Lycaena phlaeas Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of a Sn-based negative electrode plate of a lithium ion battery, which comprises the steps of taking nano tin dioxide as a core, coating a layer of mesoporous silica outside tin dioxide by hydrolyzing tetraethoxysilane to obtain a nano tin dioxide core-shell structure coated by the mesoporous silica, adding a carbon source into the nano tin dioxide core-shell structure coated by the mesoporous silica, fully mixing, roasting at high temperature to obtain a carbon-modified nano tin dioxide multilayer core-shell structure coated by the mesoporous silica as a negative electrode material, adding the negative electrode material, a conductive agent and a binder into deionized water, uniformly mixing to obtain a mixed slurry, uniformly coating the mixed slurry on the rough surface of porous copper foil, and drying to obtain the Sn-based negative electrode plate of the lithium ion battery. The Sn-based negative electrode piece prepared by the invention has the advantages of high stability, large gram capacity and good cycle performance.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a preparation method of a Sn-based negative electrode plate of a lithium ion battery.
Background
With the rapid development of mobile internet and new energy, the performance requirements of portable digital equipment and power energy on lithium ion batteries are higher and higher. In SnO2The lithium-doped lithium iron phosphate cathode material has the advantages of high theoretical capacity, moderate lithium intercalation potential and the like. But also has the defects of first irreversible capacity loss and large volume expansion, resulting in SnO in lithium intercalation and lithium deintercalation processes2The anode material breaks and cracks, resulting in poor cycle performance.
In addition, for the traditional negative pole piece, the used nonporous copper foil has small surface area, poor adsorption capacity and small load capacity on a negative pole material, so that the performance and the service life of the lithium ion battery are small. In addition, the traditional nonporous copper foil cannot give consideration to both quality and performance, and the gram capacity of the prepared negative pole piece is smaller under the same quality.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a Sn-based negative electrode plate of a lithium ion battery, and the prepared Sn-based negative electrode plate has the advantages of high stability, large gram capacity and good cycle performance.
The technical scheme of the invention is as follows:
a preparation method of a Sn-based negative electrode plate of a lithium ion battery comprises the steps of taking nano tin dioxide as a core, coating a layer of mesoporous silica outside tin dioxide through hydrolysis of ethyl orthosilicate to obtain a nano tin dioxide core-shell structure coated by the mesoporous silica, adding a carbon source into the nano tin dioxide core-shell structure coated by the mesoporous silica, fully mixing, roasting at a high temperature to obtain a carbon-modified nano tin dioxide multilayer core-shell structure coated by the mesoporous silica as a negative electrode material, weighing the negative electrode material, a conductive agent and a binder in proportion, dispersing in deionized water, uniformly stirring to obtain a mixed slurry, uniformly coating the mixed slurry on the rough surface of a porous copper foil, and performing vacuum drying at 85 ℃ to obtain the Sn-based negative electrode plate of the lithium ion battery.
The particle size of the nano tin dioxide is 50-150nm, and the aperture of the mesoporous silica is 5-50 nm; in the carbon-modified mesoporous silica-coated nano tin dioxide multilayer core-shell structure, the thickness of the silica layer structure is 60-120nm, carbon is modified on the surface and in the mesoporous of the mesoporous silica, the thickness of the carbon layer is 2-20nm, and the carbon-modified mesoporous silica still maintains the mesoporous structure.
The preparation method of the mesoporous silica coated nano tin dioxide core-shell structure specifically comprises the following steps:
(1) preparing an ethanol aqueous solution containing hexadecyl trimethyl ammonium bromide, adding nano tin dioxide powder under ultrasonic, and uniformly stirring to obtain nano tin dioxide sol;
(2) adjusting the pH value of the nano tin dioxide sol to 10, dropwise adding ethyl orthosilicate while stirring, reacting for 24 hours, and centrifugally washing to obtain the mesoporous silica coated nano tin dioxide powder.
The concentration of the nano tin dioxide sol is 0.1-0.2 g/mL.
The mass fraction of the tetraethoxysilane in the reactant is 4-7%.
The carbon source is glucose solution, the high-temperature roasting is firstly carried out for 6h at 85 ℃, and then is carried out in a tubular furnace at 450 ℃ and N2Carbonizing for 4h in the atmosphere, and finally naturally cooling to obtain the carbon-modified mesoporous silica-coated nano tin dioxide multilayer core-shell structure.
The conductive agent is a carbon nano tube, and the adhesive is polylactic acid.
The mass ratio of the negative electrode material, the carbon nano tube and the polylactic acid is 8:1: 1.
The thickness of the porous copper foil is 8-15 μm, the pore diameter is 500 μm and the pore spacing is 1000 μm and 100-.
The invention has the advantages that:
(1) the nano tin dioxide is coated by the mesoporous silicon dioxide, the volume change of the tin dioxide in the charging and discharging process can be effectively relieved, the circulation stability is improved, meanwhile, the mesoporous silicon dioxide has the advantages of large specific surface area, more pores, strong electrolyte absorption capacity and improved Li+A transmission rate;
(2) the carbon layer and the conductive agent in the nano tin dioxide multilayer core-shell structure coated by the carbon-modified mesoporous silica can effectively improve the conductivity of the Sn-based material;
(3) in the slurry mixing process, part of the conductive agent Carbon Nano Tubes (CNTs) are inserted into the mesopores of the mesoporous silica, and under the combined action of the adhesive polylactic acid, the stability of the negative electrode is effectively improved, the probability of desorption of the negative electrode material from the porous copper foil is reduced, and the stability of the negative electrode is improved;
(4) and in the coating process, the porous copper foil is used for replacing the common copper foil, so that the gram capacity of the negative electrode material is effectively improved.
Drawings
FIG. 1 is a graph showing the cycle performance test of examples of the present invention and comparative examples.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a Sn-based negative electrode plate of a lithium ion battery specifically comprises the following steps:
(1) adding 0.260g of hexadecyl trimethyl ammonium bromide (CTAB) into a mixed solution of 60mL of water and 40mL of ethanol to obtain an ethanol aqueous solution of CTAB, and adding 10g of nano tin dioxide (SnO) with the diameter of 50nm under ultrasonic2) The powder is evenly stirred to obtain the nano SnO2Sol;
(2) nano SnO2Adding ammonia water into the sol to adjust the pH value to 10, dropwise adding 5mL of tetraethoxysilane with the mass fraction of 5% under strong magnetic stirring, reacting for 24 hours, and centrifugally washing to obtain mesoporous silica coated nano tin dioxide (mSiO)2@nSnO2) Powder;
(3) to mSiO2@nSnO2Adding glucose solution into the powderMixing the above solutions, drying at 85 deg.C for 6 hr, and heating in a tube furnace at 450 deg.C under N2Carbonizing for 4 hours in the atmosphere, and finally naturally cooling to obtain a carbon-modified mesoporous silica-coated nano tin dioxide multilayer core-shell structure as a negative electrode material;
(4) and mixing the negative electrode material, Carbon Nanotubes (CNTs) and polylactic acid ((C3H4O2) n) according to the weight ratio of 8:1:1, dispersing the mixture in deionized water, and uniformly stirring to obtain mixed slurry;
(5) and uniformly coating the mixed slurry on the rough surface of a porous copper foil, wherein the thickness of the copper foil is 9 microns, the aperture is 400 microns, and the hole spacing is 500 microns, and finally, carrying out vacuum drying at 85 ℃ to obtain the Sn-based negative electrode plate.
Example 2
A preparation method of a Sn-based negative electrode plate of a lithium ion battery specifically comprises the following steps:
(1) adding 0.260g CTAB into the mixed solution of 60mL water and 40mL ethanol to obtain ethanol aqueous solution of CTAB, and adding 20g nano tin dioxide (SnO) with diameter of 50nm under ultrasonic2) The powder is evenly stirred to obtain the nano SnO2Sol;
(2) nano SnO2Adding ammonia water into the sol to adjust the pH value to 10, dropwise adding 5mL of tetraethoxysilane with the mass fraction of 5% under strong magnetic stirring, reacting for 24 hours, and centrifugally washing to obtain mesoporous silica coated nano tin dioxide (mSiO)2@nSnO2) Powder;
(3) to mSiO2@nSnO2Adding glucose solution into the powder, stirring, oven drying at 85 deg.C for 6 hr, and heating in a tube furnace at 450 deg.C under N2Carbonizing for 4 hours in the atmosphere, and finally naturally cooling to obtain a carbon-modified mesoporous silica-coated nano tin dioxide multilayer core-shell structure as a negative electrode material;
(4) and mixing the negative electrode material, CNTs and (C3H4O2) n according to the weight ratio of 8:1:1, dispersing the mixture in deionized water, and uniformly stirring to obtain mixed slurry;
(5) and uniformly coating the mixed slurry on the rough surface of a porous copper foil, wherein the thickness of the copper foil is 9 microns, the aperture is 400 microns, and the hole spacing is 500 microns, and finally, carrying out vacuum drying at 85 ℃ to obtain the Sn-based negative electrode plate.
Example 3
A preparation method of a Sn-based negative electrode plate of a lithium ion battery specifically comprises the following steps:
(1) adding 0.260g CTAB into the mixed solution of 60mL water and 40mL ethanol to obtain ethanol aqueous solution of CTAB, and adding 10g nano tin dioxide (SnO) with the diameter of 50nm under ultrasonic2) The powder is evenly stirred to obtain the nano SnO2Sol;
(2) nano SnO2Adding ammonia water into the sol to adjust the pH value to 10, dropwise adding 7mL of tetraethoxysilane with the mass fraction of 5% under strong magnetic stirring, reacting for 24 hours, and centrifugally washing to obtain mesoporous silica coated nano tin dioxide (mSiO)2@nSnO2) Powder;
(3) to mSiO2@nSnO2Adding glucose solution into the powder, stirring, oven drying at 85 deg.C for 6 hr, and heating in a tube furnace at 450 deg.C under N2Carbonizing for 4 hours in the atmosphere, and finally naturally cooling to obtain a carbon-modified mesoporous silica-coated nano tin dioxide multilayer core-shell structure as a negative electrode material;
(4) and mixing the negative electrode material, CNTs and (C3H4O2) n according to the weight ratio of 8:1:1, dispersing the mixture in deionized water, and uniformly stirring to obtain mixed slurry;
(5) and uniformly coating the mixed slurry on the rough surface of a porous copper foil, wherein the thickness of the copper foil is 9 microns, the aperture is 400 microns, and the hole spacing is 500 microns, and finally, carrying out vacuum drying at 85 ℃ to obtain the Sn-based negative electrode plate.
Comparative example
Mixing nano SnO2The powder, the conductive agent acetylene black and the binder sodium carboxymethylcellulose are weighed according to the mass ratio of 8:1:1, dispersed in deionized water and uniformly stirred to obtain mixed slurry; and uniformly coating the mixed slurry on the rough surface of a clean copper foil, and drying in vacuum at 85 ℃ to obtain the common Sn-based negative electrode plate.
Full batteries with the same specification are prepared by matching the Sn-based negative electrode plates obtained in the above examples 1, 2 and 3 and the comparative example with the same positive electrode material, and performance tests are carried out. Examples 1-3 and comparative data are shown in the following table and figure 1:
as can be seen from the above table, the Sn-based negative electrode materials prepared by the present invention all have a high energy density, as compared to the comparative examples. After 100-week circulation, the capacity retention rate of the Sn-based negative electrode material prepared by the invention is obviously higher than that of a comparative example, and the Sn-based negative electrode material has better circulation performance.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of a Sn-based negative electrode plate of a lithium ion battery is characterized by comprising the following steps: the preparation method comprises the steps of taking nano tin dioxide as a core, coating a layer of mesoporous silica outside tin dioxide by hydrolyzing tetraethoxysilane to obtain a nano tin dioxide core-shell structure coated by the mesoporous silica, adding a carbon source into the nano tin dioxide core-shell structure coated by the mesoporous silica, fully mixing, roasting at high temperature to obtain a carbon-modified nano tin dioxide multilayer core-shell structure coated by the mesoporous silica as a negative electrode material, weighing the negative electrode material, a conductive agent and a binder in proportion, dispersing in deionized water, uniformly stirring to obtain a mixed slurry, uniformly coating the mixed slurry on the rough surface of a porous copper foil, and drying in vacuum at 85 ℃ to obtain the Sn-based negative electrode piece of the lithium ion battery.
2. The preparation method of the Sn-based negative electrode plate of the lithium ion battery according to claim 1, characterized by comprising the following steps: the particle size of the nano tin dioxide is 50-150nm, and the aperture of the mesoporous silica is 5-50 nm; in the carbon-modified mesoporous silica-coated nano tin dioxide multilayer core-shell structure, the thickness of the silica layer structure is 60-120nm, carbon is modified on the surface and in the mesoporous of the mesoporous silica, the thickness of the carbon layer is 2-20nm, and the carbon-modified mesoporous silica still maintains the mesoporous structure.
3. The preparation method of the Sn-based negative electrode plate of the lithium ion battery according to claim 1, characterized by comprising the following steps: the preparation method of the mesoporous silica coated nano tin dioxide core-shell structure specifically comprises the following steps:
(1) preparing an ethanol aqueous solution containing hexadecyl trimethyl ammonium bromide, adding nano tin dioxide powder under ultrasonic, and uniformly stirring to obtain nano tin dioxide sol;
(2) adjusting the pH value of the nano tin dioxide sol to 10, dropwise adding ethyl orthosilicate while stirring, reacting for 24 hours, and centrifugally washing to obtain the mesoporous silica coated nano tin dioxide powder.
4. The preparation method of the Sn-based negative electrode plate of the lithium ion battery according to claim 3, characterized by comprising the following steps: the concentration of the nano tin dioxide sol is 0.1-0.2 g/mL.
5. The preparation method of the Sn-based negative electrode plate of the lithium ion battery according to claim 3, characterized by comprising the following steps: the mass fraction of the tetraethoxysilane in the reactant is 4-7%.
6. The preparation method of the Sn-based negative electrode plate of the lithium ion battery according to claim 1, characterized by comprising the following steps: the carbon source is glucose solution, the high-temperature roasting is firstly carried out for 6h at 85 ℃, and then is carried out in a tubular furnace at 450 ℃ and N2Carbonizing for 4h in the atmosphere, and finally naturally cooling to obtain the carbon-modified mesoporous silica-coated nano tin dioxide multilayer core-shell structure.
7. The preparation method of the Sn-based negative electrode plate of the lithium ion battery according to claim 1, characterized by comprising the following steps: the conductive agent is a carbon nano tube, and the adhesive is polylactic acid.
8. The preparation method of the Sn-based negative electrode plate of the lithium ion battery according to claim 7, characterized by comprising the following steps: the mass ratio of the negative electrode material, the carbon nano tube and the polylactic acid is 8:1: 1.
9. The preparation method of the Sn-based negative electrode plate of the lithium ion battery according to claim 1, characterized by comprising the following steps: the thickness of the porous copper foil is 8-15 μm, the pore diameter is 500 μm and the pore spacing is 1000 μm and 100-.
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