CN114335544A - Water-based binder, lithium ion battery cathode material and lithium ion battery - Google Patents
Water-based binder, lithium ion battery cathode material and lithium ion battery Download PDFInfo
- Publication number
- CN114335544A CN114335544A CN202210005016.6A CN202210005016A CN114335544A CN 114335544 A CN114335544 A CN 114335544A CN 202210005016 A CN202210005016 A CN 202210005016A CN 114335544 A CN114335544 A CN 114335544A
- Authority
- CN
- China
- Prior art keywords
- lithium
- water
- ion battery
- lithium ion
- reaction
- 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.)
- Granted
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011230 binding agent Substances 0.000 title claims abstract description 28
- 239000010406 cathode material Substances 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 239000004793 Polystyrene Substances 0.000 claims abstract description 9
- 229920002223 polystyrene Polymers 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 8
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 6
- ITCAUAYQCALGGV-XTICBAGASA-M sodium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Na+].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O ITCAUAYQCALGGV-XTICBAGASA-M 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 229910021389 graphene Inorganic materials 0.000 claims description 15
- 239000007773 negative electrode material Substances 0.000 claims description 14
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 11
- 239000011267 electrode slurry Substances 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000006258 conductive agent Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000002077 nanosphere Substances 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- ZKIAYSOOCAKOJR-UHFFFAOYSA-M lithium;2-phenylethenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 ZKIAYSOOCAKOJR-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-N sodium polysulfide Chemical compound [Na+].S HYHCSLBZRBJJCH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 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 claims 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract description 2
- CMBMVZDLQOJGIJ-UHFFFAOYSA-N lithium;styrene Chemical compound [Li].C=CC1=CC=CC=C1 CMBMVZDLQOJGIJ-UHFFFAOYSA-N 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 238000009792 diffusion process Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 239000003273 ketjen black Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 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 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 244000207740 Lemna minor Species 0.000 description 1
- 235000006439 Lemna minor Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000001855 Portulaca oleracea Nutrition 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- FBDMJGHBCPNRGF-UHFFFAOYSA-M [OH-].[Li+].[O-2].[Mn+2] Chemical compound [OH-].[Li+].[O-2].[Mn+2] FBDMJGHBCPNRGF-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003013 cathode binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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)
Abstract
The invention relates to the technical field of lithium batteries, in particular to a water system binder, a lithium ion battery cathode material and a lithium ion battery, wherein the water system binder is a polystyrene lithium sulfonate-butadiene emulsion, water, disproportionated sodium abietate, styrene lithium sulfonate, an initiator and sodium phosphate are added into a reaction kettle during preparation, the temperature is reduced and the vacuum degree is vacuumized to be-0.1 to-0.08 MPa in the kettle, butadiene is introduced for reaction for 4 to 7 hours, tert-dodecyl mercaptan is added for reaction for 1 to 2 hours, a terminator is added, the stirring reaction is continued for 0.5 to 1 hour, the temperature is increased to 20 to 30 ℃, the vacuum degree in the kettle is adjusted to be-0.05 to-0.03 MPa, the stirring reaction is continued for 0.5 to 1 hour, the prepared cathode material has better circulation stability under the current density of 5C multiplying power, and still keeps higher reversible capacity even after 1000 times of charging and discharging, and the capacity retention rate is more than or equal to 90 percent.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a water-based binder, a lithium ion battery cathode material and a lithium ion battery.
Background
The lithium ion battery is used as an active power source of the new energy automobile, and the performance of the lithium ion battery directly determines the performance of the new energy automobile. The time for replenishing fuel for a traditional fuel vehicle is generally 2-5 minutes, while the charging time of the current electric vehicle is 1 hour at least and more than 8 hours. The quick charging performance of the single battery cell determines the quick charging performance of the battery pack, so that the improvement of the quick charging performance of the single battery cell is the latest research direction of various battery manufacturers.
Document 1: research on the measurement of lithium ion diffusion coefficient [ J ] in graphite electrode by the voltage constant-current charge capacity ratio method in tangxincun, allen duckweed, old jade article, xiaxi, the report of physicochemical science, 2002 (stage 8) shows that: the solid-phase diffusion of lithium ions in the graphite is a control step of the whole electrode reaction process, and in the lithium battery processing process, the graphite is wrapped by the organic binder, so that the solid-phase diffusion rate of the lithium ions in the graphite is reduced, the polarization of the charging process is increased, the charging speed is slowed, and the diffusion rate of the lithium ions in the graphite is improved, so that the quick charging performance of the lithium battery can be fundamentally improved.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention provides a water-based binder, a lithium ion battery negative electrode material and a lithium ion battery.
The adopted technical scheme is as follows:
the invention provides a water-based binder, which is a lithium polystyrene sulfonate-butadiene emulsion.
Further, the preparation method of the lithium polystyrene sulfonate-butadiene emulsion comprises the following steps:
s1: adding water, disproportionated sodium abietate, lithium styrene sulfonate, an initiator and sodium phosphate into a reaction kettle;
s2: sealing the reaction kettle, cooling to 0-5 ℃, and vacuumizing to ensure that the vacuum degree in the kettle is-0.1 to-0.08 MPa;
s3: starting stirring, filling gas butadiene into the reaction kettle, and reacting for 4-7 h;
s4: adding tert-dodecyl mercaptan, and continuously stirring for reaction for 1-2 h;
s5: adding a terminator, and continuously stirring and reacting for 0.5-1 h;
s6: heating to 20-30 ℃, adjusting the vacuum degree in the kettle to-0.05-0.03 MPa, continuously stirring for reaction for 0.5-1 h, and then grinding and deironing to obtain the lithium polystyrene sulfonate-butadiene emulsion.
Further, the initiator is one or more of cumene hydroperoxide, rongalite and disodium ethylene diamine tetraacetate.
Further, the terminating agent is one or more of sodium dimethyldithiocarbamate, sodium nitrite, sodium polysulfide and polyethylene polyamine.
Further, the mass ratio of the lithium styrene sulfonate, the butadiene, the disproportionated sodium abietate, the initiator, the sodium phosphate, the tert-dodecyl mercaptan and the terminator is 189.1: 54-108: 4.62: 0.04-0.10: 0.24-0.45: 0.16: 0.02-0.05.
The invention also provides a lithium ion battery cathode material which comprises the aqueous binder.
Further, the lithium ion battery cathode material also comprises a nano carbon sphere/graphene compound, lithium titanate and a conductive agent.
The conductive agent in the invention is a common conductive agent in the market, and the type can be selected from SPUER Li, S-O, KS-6, KS-15, SFG-6, SFG-15, 350G, Acetylene Black (AB), Ketjen Black (KB), Vapor Grown Carbon Fiber (VGCF), Carbon Nano Tube (CNT) and the like.
Further, the preparation method of the nano carbon sphere/graphene composite comprises the following steps:
adding a glucose solution with the concentration of 0.1-0.5 mol/L into a hydrothermal reaction kettle, heating to 180-200 ℃ for hydrothermal reaction for 4-6 h, separating precipitates generated by the reaction after the reaction is finished, washing with acetone, ethanol and water in sequence, drying, grinding to obtain carbon nanospheres, adding the carbon nanospheres and graphene into water, carrying out ultrasonic oscillation for 30-50 min, adding the solution into the hydrothermal reaction kettle, reacting at the pressure of 2-2.5 MPa and the temperature of 180-200 ℃ for 30-50 min, carrying out precipitation separation, washing with water, and drying.
Further, the preparation method of the lithium ion battery negative electrode material comprises the following steps:
dispersing titanium dioxide, lithium hydroxide and a carbon nanosphere/graphene compound in water, ultrasonically oscillating for 2-4 hours, then drying the mixture in vacuum at 110-120 ℃ for 6-10 hours, then grinding, then calcining at 700-750 ℃ for 8-10 hours to obtain an active material, mixing the active material, a conductive agent and a water-based binder, ultrasonically stirring for 8-10 hours to obtain negative electrode slurry, then uniformly coating the negative electrode slurry on the surface of a conductive substrate, and vacuum drying to remove a solvent.
The invention provides a lithium ion battery, which comprises the lithium ion battery cathode material.
The invention has the beneficial effects that:
the aqueous binder can be used for replacing the currently common lithium ion battery cathode binder, the polystyrene lithium sulfonate-butadiene emulsion can release lithium ions under the dissolution of the lithium ion battery electrolyte, the released lithium ions can play a relay role when the battery is charged, and can be diffused more quickly under the action of an electric field, so that the quick charging performance of the lithium ion battery is improved, the preparation process is simple, the required equipment is market mature equipment, the production process is pollution-free, the nano carbon spheres/graphene composite introduces the nano carbon spheres between graphene sheet layers, the lithium storage performance of the cathode material can be further improved, the nano carbon spheres not only can provide larger specific surface and shorter diffusion distance, but also can prevent the agglomeration of active particles, and provide enough space to relieve the volume expansion, and tests show that, the negative electrode material prepared by the invention has good cycling stability under the current density of 5C multiplying power, high reversible capacity can be still maintained even after 1000 times of charging and discharging, and the capacity retention rate is more than or equal to 90%.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
a water-based binder is prepared by the following steps:
adding 280kg of water, 4.62kg of disproportionated sodium abietate, 189.1kg of lithium styrene sulfonate, 0.06kg of rongalite and 0.3kg of sodium phosphate into a reaction kettle, sealing the reaction kettle, stirring, cooling to 0-5 ℃, vacuumizing to ensure that the vacuum degree in the kettle is-0.1 MPa, filling 80kg of gaseous butadiene into the reaction kettle, reacting for 6 hours, adding 0.16kg of tert-dodecyl mercaptan, continuously stirring for reaction for 2 hours, adding 0.04kg of sodium nitrite, continuously stirring for reaction for 1 hour, heating to 25 ℃, adjusting the vacuum degree in the kettle to-0.05 MPa, recovering unreacted butadiene gas, continuously stirring for 1 hour, grinding the crude liquid in the reaction kettle by a sand mill, and removing iron by an iron remover to obtain the lithium polystyrene sulfonate-butadiene emulsion.
A lithium ion battery negative electrode material includes:
50g of nano carbon sphere/graphene compound, 5g of lithium titanate, 10g of conductive agent KB and 25g of water-based binder.
The preparation method of the nano carbon sphere/graphene composite comprises the following steps:
adding a glucose solution with the concentration of 0.2mol/L into a hydrothermal reaction kettle, heating to 200 ℃ for hydrothermal reaction for 4 hours, separating precipitates generated by the reaction after the reaction is finished, washing with acetone, ethanol and water in sequence, drying, grinding to obtain carbon nanospheres, adding the carbon nanospheres and graphene into water according to the mass ratio of 1:1, carrying out ultrasonic oscillation for 40 minutes, adding the solution into the hydrothermal reaction kettle, reacting for 50 minutes at the pressure of 2.5MPa and 190 ℃, carrying out precipitation separation, washing with water, and drying.
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
dispersing 4.4g of titanium dioxide, 1.06g of lithium hydroxide and 50g of a nano carbon sphere/graphene compound in water, ultrasonically oscillating for 4 hours, then drying the mixture in vacuum at 120 ℃ for 10 hours, grinding the mixture, then calcining the mixture at 750 ℃ for 10 hours to obtain an active material, mixing the active material, a conductive agent KB and a water-based binder, ultrasonically stirring the mixture for 10 hours to obtain negative electrode slurry, then uniformly coating the negative electrode slurry on the surface of a copper foil current collector, and vacuum drying the mixture to remove a solvent.
Example 2:
essentially the same as in example 1, except that the initiator was replaced with cumene hydroperoxide.
Example 3:
essentially the same as in example 1, except that the terminator was replaced with sodium dimethyldithiocarbamate.
Example 4:
substantially the same as in example 1 except that a lithium ion battery negative electrode material comprises:
65g of artificial graphite and 25g of water-based binder.
Mixing artificial graphite and a water-based binder, ultrasonically stirring for 10h to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of a copper foil current collector, and performing vacuum drying to remove a solvent.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that the lithium ion battery negative electrode material does not contain lithium titanate.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that lithium titanate is directly added.
The preparation method of the lithium ion battery negative electrode material comprises the following steps:
mixing lithium titanate, a nano carbon sphere/graphene compound, a conductive agent KB and a water-based binder, ultrasonically stirring for 10 hours to obtain negative electrode slurry, uniformly coating the negative electrode slurry on the surface of a copper foil current collector, and performing vacuum drying to remove a solvent.
Comparative example 3
Comparative example 3 is substantially the same as example 1 except that the aqueous binder was replaced with a 10 wt% sodium carboxymethylcellulose solution.
Comparative example 4
Comparative example 4 is substantially the same as example 1 except that the aqueous binder is replaced with styrene-butadiene rubber emulsion.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that the water-based binder was replaced with a 10 wt% polyvinyl alcohol solution.
Comparative example 6
Comparative example 6 is substantially the same as example 4 except that the aqueous binder was replaced with a 10 wt% sodium carboxymethylcellulose solution.
And (3) performance testing:
the cathode materials prepared in the embodiments 1-4 and the comparative examples 1-6 of the invention are used as the cathode of the CR2032 lithium manganese battery to carry out the tests of the charge-discharge specific capacity and the cycle performance,
the assembled CR2032 lithium manganese dioxide battery is subjected to constant-current charge and discharge test by using a CT2001A type blue light test system, and data such as charge and discharge specific capacity, cyclic specific capacity and the like of the electrode material can be obtained through the constant-current charge and discharge test. And (3) testing conditions are as follows: the charge cut-off voltage was 3V, the discharge cut-off voltage was 1V, the current density was 5C rate (1℃ ═ 160mA/g), and the test temperature was 25 ± 1 ℃.
The results are shown in table 1 below:
table 1:
according to the tests, the prepared negative electrode material has better cycle stability under the current density of 5C multiplying power, and can still maintain higher reversible capacity even after 1000 times of charge and discharge, and the capacity retention rate is more than or equal to 90%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The water-based binder is characterized in that the water-based binder is a lithium polystyrene sulfonate-butadiene emulsion.
2. The aqueous binder according to claim 1, wherein the lithium polystyrene sulfonate-butadiene emulsion is prepared by a method comprising:
s1: adding water, disproportionated sodium abietate, lithium styrene sulfonate, an initiator and sodium phosphate into a reaction kettle;
s2: sealing the reaction kettle, cooling to 0-5 ℃, and vacuumizing to ensure that the vacuum degree in the kettle is-0.1 to-0.08 MPa;
s3: starting stirring, filling gas butadiene into the reaction kettle, and reacting for 4-7 h;
s4: adding tert-dodecyl mercaptan, and continuously stirring for reaction for 1-2 h;
s5: adding a terminator, and continuously stirring and reacting for 0.5-1 h;
s6: heating to 20-30 ℃, adjusting the vacuum degree in the kettle to-0.05-0.03 MPa, continuously stirring for reaction for 0.5-1 h, and then grinding and deironing to obtain the lithium polystyrene sulfonate-butadiene emulsion.
3. The aqueous binder as claimed in claim 2, wherein the initiator is one or more selected from cumene hydroperoxide, rongalite and disodium ethylenediaminetetraacetate.
4. The aqueous binder of claim 2 wherein the terminating agent is one or more selected from the group consisting of sodium dimethyldithiocarbamate, sodium nitrite, sodium polysulfide, and polyethylene polyamine.
5. The water-based adhesive according to claim 2, wherein the mass ratio of the lithium styrene sulfonate, the butadiene, the sodium disproportionated rosin acid, the initiator, the sodium phosphate, the tert-dodecyl mercaptan, and the terminating agent is 189.1: 54-108: 4.62: 0.04-0.10: 0.24-0.45: 0.16: 0.02-0.05.
6. A negative electrode material for a lithium ion battery, comprising the aqueous binder according to claim 1.
7. The negative electrode material of a lithium ion battery as claimed in claim 6, further comprising a nanocarbon sphere/graphene composite, lithium titanate, and a conductive agent.
8. The negative electrode material of the lithium ion battery of claim 1, wherein the preparation method of the nano carbon sphere/graphene composite is as follows:
adding a glucose solution with the concentration of 0.1-0.5 mol/L into a hydrothermal reaction kettle, heating to 180-200 ℃ for hydrothermal reaction for 4-6 h, separating precipitates generated by the reaction after the reaction is finished, washing with acetone, ethanol and water in sequence, drying, grinding to obtain carbon nanospheres, adding the carbon nanospheres and graphene into water, carrying out ultrasonic oscillation for 30-50 min, adding the solution into the hydrothermal reaction kettle, reacting at the pressure of 2-2.5 MPa and the temperature of 180-200 ℃ for 30-50 min, carrying out precipitation separation, washing with water, and drying.
9. The negative electrode material of a lithium ion battery according to claim 8, which is prepared by the following method:
dispersing titanium dioxide, lithium hydroxide and a carbon nanosphere/graphene compound in water, ultrasonically oscillating for 2-4 hours, then drying the mixture in vacuum at 110-120 ℃ for 6-10 hours, then grinding, then calcining at 700-750 ℃ for 8-10 hours to obtain an active material, mixing the active material, a conductive agent and a water-based binder, ultrasonically stirring for 8-10 hours to obtain negative electrode slurry, then uniformly coating the negative electrode slurry on the surface of a conductive substrate, and vacuum drying to remove a solvent.
10. A lithium ion battery comprising the lithium ion battery negative electrode material according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210005016.6A CN114335544B (en) | 2022-01-05 | 2022-01-05 | Water-based binder, lithium ion battery negative electrode material and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210005016.6A CN114335544B (en) | 2022-01-05 | 2022-01-05 | Water-based binder, lithium ion battery negative electrode material and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114335544A true CN114335544A (en) | 2022-04-12 |
| CN114335544B CN114335544B (en) | 2024-07-05 |
Family
ID=81024728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210005016.6A Active CN114335544B (en) | 2022-01-05 | 2022-01-05 | Water-based binder, lithium ion battery negative electrode material and lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114335544B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114927692A (en) * | 2022-05-30 | 2022-08-19 | 远景动力技术(江苏)有限公司 | Binder for negative electrode material and electrochemical device |
| CN115572557A (en) * | 2022-10-11 | 2023-01-06 | 珠海冠宇电池股份有限公司 | Binder and battery comprising same |
Citations (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0375446A1 (en) * | 1988-12-21 | 1990-06-27 | Exxon Research And Engineering Company | Adhesive composition |
| JP2002363228A (en) * | 2001-06-08 | 2002-12-18 | Takeda Chem Ind Ltd | Latex composition and method for producing the same |
| KR20040013556A (en) * | 2002-08-07 | 2004-02-14 | 이완진 | Method for the preparation of lithiumated/sulfonated styrene-hydrodien copolymer and multiporous polymer electrolyte composition for a lithium polymer secondary battery including the copolymer |
| KR100574639B1 (en) * | 2004-11-08 | 2006-04-27 | 전남대학교산학협력단 | Sulfonated compound binder for lithium polymer battery, composite electrode comprising the same, and lithium polymer battery comprising the said composite electrode |
| CN101228192A (en) * | 2005-07-22 | 2008-07-23 | 克雷顿聚合物研究公司 | Sulfonated block copolymers, method for making same, and various uses for such block copolymers |
| WO2008097723A1 (en) * | 2007-02-06 | 2008-08-14 | 3M Innovative Properties Company | Electrodes including novel binders and methods of making and using the same |
| JP2009059514A (en) * | 2007-08-30 | 2009-03-19 | Sony Corp | Negative electrode and battery |
| WO2010113940A1 (en) * | 2009-03-30 | 2010-10-07 | Jsr株式会社 | Composition for electrochemical-device electrode binder, electrode slurry for electrochemical device, and electrode for electrochemical device |
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
| CN102509643A (en) * | 2011-11-29 | 2012-06-20 | 西北师范大学 | Graphene/carbon ball composite material, and preparation and application thereof |
| CN103074007A (en) * | 2012-12-27 | 2013-05-01 | 上海交通大学 | Water-based adhesive used in silicon anode of lithium ion battery and preparation method of silicon anode |
| JP2013225497A (en) * | 2012-03-19 | 2013-10-31 | Yokohama National Univ | Alkali metal-sulfur secondary battery |
| CN103545526A (en) * | 2013-09-25 | 2014-01-29 | 东莞市翔丰华电池材料有限公司 | Preparation method of aqueous lanthanum-doped lithium titanate anode paste |
| CN104170130A (en) * | 2012-11-19 | 2014-11-26 | 株式会社Lg化学 | Cathode active material composition and lithium secondary battery comprising same |
| CN105336961A (en) * | 2015-11-30 | 2016-02-17 | 四川北方硝化棉股份有限公司 | Lithium battery anode and preparation method thereof |
| CN106366246A (en) * | 2016-08-29 | 2017-02-01 | 江苏亚泰化工有限公司 | Pyridine-styrene-butadiene rubber latex and preparation method thereof |
| CN107369835A (en) * | 2016-05-12 | 2017-11-21 | 华为技术有限公司 | A kind of lithium ion battery conductive adhesive and preparation method thereof, lithium ion battery electrode piece and preparation method and lithium ion battery |
| CN107925037A (en) * | 2015-08-20 | 2018-04-17 | 日本瑞翁株式会社 | Non-aqueous secondary battery adhesive composition, non-aqueous secondary battery functional layer composition, non-aqueous secondary battery functional layer and non-aqueous secondary battery |
| CN108064423A (en) * | 2015-08-31 | 2018-05-22 | 株式会社Lg化学 | For the adhesive for including magnetic material of secondary cell |
| JP2018142451A (en) * | 2017-02-28 | 2018-09-13 | 三洋化成工業株式会社 | Battery electrode binder |
| CN108598482A (en) * | 2018-04-02 | 2018-09-28 | 合肥国轩高科动力能源有限公司 | Carbon black modified water-based SBR lithium ion battery binder and preparation method thereof |
| JP2018160397A (en) * | 2017-03-23 | 2018-10-11 | 三洋化成工業株式会社 | Battery electrode binder |
| CN109360976A (en) * | 2018-12-03 | 2019-02-19 | 重庆力宏精细化工有限公司 | A kind of negative electrode material of lithium battery and its preparation method and application |
| CN110061188A (en) * | 2019-03-19 | 2019-07-26 | 长沙市秒冲电池技术与材料研究所 | Anode pole piece, cathode pole piece and high magnification fast charge lithium ion battery |
| CN110233241A (en) * | 2019-07-08 | 2019-09-13 | 无锡市明杨新能源有限公司 | Fast charging type lithium ion battery |
| CN110574195A (en) * | 2017-04-21 | 2019-12-13 | 三洋化成工业株式会社 | Binder for lithium ion electrode, electrode for lithium ion battery, and method for producing electrode for lithium ion battery |
| CN110616055A (en) * | 2018-06-20 | 2019-12-27 | 深圳市贝特瑞新能源材料股份有限公司 | Water-based binder and preparation method and application thereof |
| CN111900393A (en) * | 2020-06-24 | 2020-11-06 | 珠海冠宇电池股份有限公司 | High-ionic-conductivity binder and lithium ion battery containing same |
| CN112029452A (en) * | 2020-09-10 | 2020-12-04 | 华鼎国联四川电池材料有限公司 | Preparation method and application of adhesive capable of improving battery rate performance |
| CN112279982A (en) * | 2020-10-29 | 2021-01-29 | 珠海冠宇电池股份有限公司 | Binder for silicon-based negative electrode and lithium ion battery containing same |
| US20210155484A1 (en) * | 2019-11-26 | 2021-05-27 | Global Graphene Group, Inc. | Combined graphene balls and metal particles for an anode of an alkali metal battery |
| CN112864387A (en) * | 2021-01-04 | 2021-05-28 | 昆山宝创新能源科技有限公司 | Negative electrode slurry and preparation method and application thereof |
-
2022
- 2022-01-05 CN CN202210005016.6A patent/CN114335544B/en active Active
Patent Citations (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0375446A1 (en) * | 1988-12-21 | 1990-06-27 | Exxon Research And Engineering Company | Adhesive composition |
| JP2002363228A (en) * | 2001-06-08 | 2002-12-18 | Takeda Chem Ind Ltd | Latex composition and method for producing the same |
| KR20040013556A (en) * | 2002-08-07 | 2004-02-14 | 이완진 | Method for the preparation of lithiumated/sulfonated styrene-hydrodien copolymer and multiporous polymer electrolyte composition for a lithium polymer secondary battery including the copolymer |
| KR100574639B1 (en) * | 2004-11-08 | 2006-04-27 | 전남대학교산학협력단 | Sulfonated compound binder for lithium polymer battery, composite electrode comprising the same, and lithium polymer battery comprising the said composite electrode |
| CN101228192A (en) * | 2005-07-22 | 2008-07-23 | 克雷顿聚合物研究公司 | Sulfonated block copolymers, method for making same, and various uses for such block copolymers |
| WO2008097723A1 (en) * | 2007-02-06 | 2008-08-14 | 3M Innovative Properties Company | Electrodes including novel binders and methods of making and using the same |
| JP2009059514A (en) * | 2007-08-30 | 2009-03-19 | Sony Corp | Negative electrode and battery |
| WO2010113940A1 (en) * | 2009-03-30 | 2010-10-07 | Jsr株式会社 | Composition for electrochemical-device electrode binder, electrode slurry for electrochemical device, and electrode for electrochemical device |
| CN102206286A (en) * | 2011-05-16 | 2011-10-05 | 北京理工大学 | Preparation method of lithium carboxymethyl cellulose for lithium battery |
| CN102509643A (en) * | 2011-11-29 | 2012-06-20 | 西北师范大学 | Graphene/carbon ball composite material, and preparation and application thereof |
| JP2013225497A (en) * | 2012-03-19 | 2013-10-31 | Yokohama National Univ | Alkali metal-sulfur secondary battery |
| CN104170130A (en) * | 2012-11-19 | 2014-11-26 | 株式会社Lg化学 | Cathode active material composition and lithium secondary battery comprising same |
| CN103074007A (en) * | 2012-12-27 | 2013-05-01 | 上海交通大学 | Water-based adhesive used in silicon anode of lithium ion battery and preparation method of silicon anode |
| CN103545526A (en) * | 2013-09-25 | 2014-01-29 | 东莞市翔丰华电池材料有限公司 | Preparation method of aqueous lanthanum-doped lithium titanate anode paste |
| CN107925037A (en) * | 2015-08-20 | 2018-04-17 | 日本瑞翁株式会社 | Non-aqueous secondary battery adhesive composition, non-aqueous secondary battery functional layer composition, non-aqueous secondary battery functional layer and non-aqueous secondary battery |
| CN108064423A (en) * | 2015-08-31 | 2018-05-22 | 株式会社Lg化学 | For the adhesive for including magnetic material of secondary cell |
| CN105336961A (en) * | 2015-11-30 | 2016-02-17 | 四川北方硝化棉股份有限公司 | Lithium battery anode and preparation method thereof |
| CN107369835A (en) * | 2016-05-12 | 2017-11-21 | 华为技术有限公司 | A kind of lithium ion battery conductive adhesive and preparation method thereof, lithium ion battery electrode piece and preparation method and lithium ion battery |
| CN106366246A (en) * | 2016-08-29 | 2017-02-01 | 江苏亚泰化工有限公司 | Pyridine-styrene-butadiene rubber latex and preparation method thereof |
| JP2018142451A (en) * | 2017-02-28 | 2018-09-13 | 三洋化成工業株式会社 | Battery electrode binder |
| JP2018160397A (en) * | 2017-03-23 | 2018-10-11 | 三洋化成工業株式会社 | Battery electrode binder |
| CN110574195A (en) * | 2017-04-21 | 2019-12-13 | 三洋化成工业株式会社 | Binder for lithium ion electrode, electrode for lithium ion battery, and method for producing electrode for lithium ion battery |
| CN108598482A (en) * | 2018-04-02 | 2018-09-28 | 合肥国轩高科动力能源有限公司 | Carbon black modified water-based SBR lithium ion battery binder and preparation method thereof |
| CN110616055A (en) * | 2018-06-20 | 2019-12-27 | 深圳市贝特瑞新能源材料股份有限公司 | Water-based binder and preparation method and application thereof |
| CN109360976A (en) * | 2018-12-03 | 2019-02-19 | 重庆力宏精细化工有限公司 | A kind of negative electrode material of lithium battery and its preparation method and application |
| CN110061188A (en) * | 2019-03-19 | 2019-07-26 | 长沙市秒冲电池技术与材料研究所 | Anode pole piece, cathode pole piece and high magnification fast charge lithium ion battery |
| CN110233241A (en) * | 2019-07-08 | 2019-09-13 | 无锡市明杨新能源有限公司 | Fast charging type lithium ion battery |
| US20210155484A1 (en) * | 2019-11-26 | 2021-05-27 | Global Graphene Group, Inc. | Combined graphene balls and metal particles for an anode of an alkali metal battery |
| CN111900393A (en) * | 2020-06-24 | 2020-11-06 | 珠海冠宇电池股份有限公司 | High-ionic-conductivity binder and lithium ion battery containing same |
| WO2021259084A1 (en) * | 2020-06-24 | 2021-12-30 | 珠海冠宇电池股份有限公司 | Binder having high ionic conductivity, and lithium ion battery containing same |
| CN112029452A (en) * | 2020-09-10 | 2020-12-04 | 华鼎国联四川电池材料有限公司 | Preparation method and application of adhesive capable of improving battery rate performance |
| CN112279982A (en) * | 2020-10-29 | 2021-01-29 | 珠海冠宇电池股份有限公司 | Binder for silicon-based negative electrode and lithium ion battery containing same |
| CN112864387A (en) * | 2021-01-04 | 2021-05-28 | 昆山宝创新能源科技有限公司 | Negative electrode slurry and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王久芬主编: "《高聚物合成工艺》", 31 July 2005, 国防工业出版社, pages: 78 - 86 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114927692A (en) * | 2022-05-30 | 2022-08-19 | 远景动力技术(江苏)有限公司 | Binder for negative electrode material and electrochemical device |
| CN115572557A (en) * | 2022-10-11 | 2023-01-06 | 珠海冠宇电池股份有限公司 | Binder and battery comprising same |
| CN115572557B (en) * | 2022-10-11 | 2024-04-16 | 珠海冠宇电池股份有限公司 | Adhesive and battery comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114335544B (en) | 2024-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107331867B (en) | Preparation method of nitrogen-doped porous carbon material used as negative electrode of sodium-ion battery | |
| CN109037664B (en) | N-doped carbon-coated Mo2Preparation method of C/C functional composite material and application of C/C functional composite material in lithium-sulfur battery | |
| CN110739427B (en) | Battery diaphragm material and preparation method and application thereof | |
| CN107275578B (en) | Method for manufacturing potassium ion battery cathode by adopting nitrogen-doped porous carbon material | |
| CN107785549B (en) | Preparation method of carbon composite negative electrode material and carbon composite negative electrode material | |
| CN112751075B (en) | Lithium ion battery and preparation method thereof | |
| CN115101741B (en) | Nitrogen-doped graphene-coated silicon-carbon composite material and preparation method and application thereof | |
| CN114552125B (en) | Nondestructive lithium supplement composite diaphragm and preparation method and application thereof | |
| CN113036146B (en) | Carbon nano tube conductive slurry and preparation method and application thereof | |
| CN114335544B (en) | Water-based binder, lithium ion battery negative electrode material and lithium ion battery | |
| CN113823781A (en) | Composite negative electrode material and preparation method thereof | |
| CN112133916A (en) | Silicon-based negative electrode material binder of lithium ion battery and preparation method and application thereof | |
| CN111900398A (en) | Magnesium-doped vanadium pentoxide nanoribbon positive electrode material, preparation method thereof and water-based zinc ion battery | |
| CN113690420B (en) | Nitrogen-sulfur doped silicon-carbon composite material and preparation method and application thereof | |
| CN107742710B (en) | Preparation method of chromium-based lithium ion battery composite negative electrode material | |
| CN103730631B (en) | A kind of lithium ion battery cathode material and its preparation method | |
| CN111477854B (en) | Composite nano material and preparation method and application thereof | |
| CN113772718A (en) | SnS-SnS2@ GO heterostructure composite material and preparation method and application thereof | |
| CN110600710B (en) | Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery | |
| CN111952566A (en) | Rubidium-doped high-rate lithium battery positive electrode material and preparation method thereof | |
| CN108155022B (en) | Preparation method of lithium ion capacitor using microcrystalline graphite material | |
| CN116014128A (en) | Lithium battery negative electrode material and preparation method thereof | |
| CN109802122B (en) | High-stability organic sodium-ion battery positive electrode material and process and application thereof | |
| CN113991107A (en) | Preparation method of zinc oxide/carbon nanotube electrode material | |
| CN112408328A (en) | Novel ZrMn-based hydride composite negative electrode material of lithium ion battery and preparation method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |