CN117199326A - Negative electrode material for sodium ion battery, negative electrode piece and sodium ion battery - Google Patents
Negative electrode material for sodium ion battery, negative electrode piece and sodium ion battery Download PDFInfo
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- CN117199326A CN117199326A CN202311445666.3A CN202311445666A CN117199326A CN 117199326 A CN117199326 A CN 117199326A CN 202311445666 A CN202311445666 A CN 202311445666A CN 117199326 A CN117199326 A CN 117199326A
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- negative electrode
- sodium
- ion battery
- sodium ion
- electrode material
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 155
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 94
- 239000006259 organic additive Substances 0.000 claims abstract description 79
- 239000011734 sodium Substances 0.000 claims abstract description 72
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 68
- 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 abstract description 49
- 125000000524 functional group Chemical group 0.000 claims abstract description 40
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 15
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 14
- 239000004305 biphenyl Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims description 49
- 230000000996 additive effect Effects 0.000 claims description 49
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 45
- 239000011230 binding agent Substances 0.000 claims description 34
- 239000006258 conductive agent Substances 0.000 claims description 34
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 29
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 29
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 29
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 29
- 235000012735 amaranth Nutrition 0.000 claims description 27
- 240000001592 Amaranthus caudatus Species 0.000 claims description 26
- 235000009328 Amaranthus caudatus Nutrition 0.000 claims description 26
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- 239000004178 amaranth Substances 0.000 claims description 26
- 229910021385 hard carbon Inorganic materials 0.000 claims description 25
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 23
- 239000006229 carbon black Substances 0.000 claims description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 235000012730 carminic acid Nutrition 0.000 claims description 6
- 239000003086 colorant Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 239000006183 anode active material Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- 229920002907 Guar gum Polymers 0.000 claims description 2
- 235000010643 Leucaena leucocephala Nutrition 0.000 claims description 2
- 240000007472 Leucaena leucocephala Species 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000000665 guar gum Substances 0.000 claims description 2
- 235000010417 guar gum Nutrition 0.000 claims description 2
- 229960002154 guar gum Drugs 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 239000003792 electrolyte Substances 0.000 abstract description 17
- 238000003860 storage Methods 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 6
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 4
- 238000012546 transfer Methods 0.000 abstract description 3
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 28
- 239000011889 copper foil Substances 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- 239000011267 electrode slurry Substances 0.000 description 22
- 239000002904 solvent Substances 0.000 description 20
- 235000019241 carbon black Nutrition 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001035 drying Methods 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000003825 pressing Methods 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000009966 trimming Methods 0.000 description 10
- 238000003466 welding Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000007600 charging Methods 0.000 description 8
- 125000006269 biphenyl-2-yl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C1=C(*)C([H])=C([H])C([H])=C1[H] 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- OIQPTROHQCGFEF-UHFFFAOYSA-L chembl1371409 Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 OIQPTROHQCGFEF-UHFFFAOYSA-L 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- -1 4-sulfophenyl Chemical group 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 2
- WLDHEUZGFKACJH-ZRUFZDNISA-K Amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1\N=N\C1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-ZRUFZDNISA-K 0.000 description 1
- 241000561734 Celosia cristata Species 0.000 description 1
- 244000124209 Crocus sativus Species 0.000 description 1
- 235000015655 Crocus sativus Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical group [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- CEZCCHQBSQPRMU-UHFFFAOYSA-L chembl174821 Chemical compound [Na+].[Na+].COC1=CC(S([O-])(=O)=O)=C(C)C=C1N=NC1=C(O)C=CC2=CC(S([O-])(=O)=O)=CC=C12 CEZCCHQBSQPRMU-UHFFFAOYSA-L 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- HSXUHWZMNJHFRV-QIKYXUGXSA-L orange G Chemical compound [Na+].[Na+].OC1=CC=C2C=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1\N=N\C1=CC=CC=C1 HSXUHWZMNJHFRV-QIKYXUGXSA-L 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 235000012731 ponceau 4R Nutrition 0.000 description 1
- 239000004175 ponceau 4R Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000013974 saffron Nutrition 0.000 description 1
- 239000004248 saffron Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- NJPKYOIXTSGVAN-UHFFFAOYSA-K trisodium;naphthalene-1,3,6-trisulfonate Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC(S([O-])(=O)=O)=CC2=CC(S(=O)(=O)[O-])=CC=C21 NJPKYOIXTSGVAN-UHFFFAOYSA-K 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a negative electrode material for a sodium ion battery, a negative electrode plate and a sodium ion battery, and belongs to the technical field of batteries; the organic additive contains at least 2 sodium sulfonate groups, at least 1 biphenyl functional group and at least 1 azo functional group, and the benzene ring is conjugated with the azo functional group. The organic additive adopted by the invention contains biphenyl and azo functional groups, the benzene rings and the benzene rings are conjugated with the azo functional groups, a large delocalized pi bond can be formed, the biphenyl functional groups have rigidity, the expansion of the anode material in the sodium intercalation and deintercalation process can be inhibited, in addition, sodium sulfonate groups can be adsorbed on the anode surface, the transfer of sodium ions on the anode surface can be accelerated, and the consumption of electrolyte and active sodium ions on the anode surface during the formation of a sodium ion battery can be reduced. Therefore, the addition of the organic additive can comprehensively improve the initial efficiency, the cycle and the high-temperature storage life of the sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a negative electrode material for a sodium ion battery, a negative electrode plate and a sodium ion battery.
Background
The lithium ion battery is widely applied to the fields of mobile electronic equipment, electric automobiles, unmanned aerial vehicles and the like due to the characteristics of high energy density, long service life, no memory effect and the like. With the continuous development of products powered by lithium ion batteries, higher demands are being placed on the energy density, lifetime, and fast charge performance of lithium ion batteries.
However, lithium has limited reserves on the earth, and high cost and low cost, and can restrict the long-term application of the lithium battery. The main element sodium in the sodium ion battery has abundant reserves on the earth, and one of the raw materials of sodium carbonate has low price and obvious cost advantage.
The common negative electrode material of the sodium ion battery is a hard carbon material, but the hard carbon material consumes more sodium ions due to the large specific surface area during formation, so that the initial effect is very low, in addition, the sodium storage curve of the hard carbon negative electrode material comprises a slope area and a platform area, the platform area corresponds to intercalation reaction of sodium ions, the low sodium ion diffusion coefficient of the platform area can deteriorate the quick charge performance of the sodium ion battery, and in addition, an interface film containing sodium on the surface of the negative electrode material at high temperature is easy to dissolve in electrolyte, so that the interface needs repeated repair, and the high temperature performance is deteriorated.
Therefore, how to efficiently improve the first effect, cycle and high-temperature storage life of sodium ion batteries is a hot spot of current research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a negative electrode material for a sodium ion battery, a negative electrode piece and a sodium ion battery. According to the invention, the organic additive is added into the negative electrode material for the sodium ion battery, the organic additive contains biphenyl and azo functional groups, benzene rings are conjugated with the azo functional groups, a large delocalized pi bond can be formed, the biphenyl functional groups have rigidity, the expansion of the negative electrode material in the sodium intercalation and deintercalation process can be inhibited, in addition, the sodium sulfonate group can be adsorbed on the surface of the negative electrode, the transfer of sodium ions on the surface of the negative electrode can be accelerated, and the consumption of electrolyte and active sodium ions on the surface of the negative electrode during the formation of the sodium ion battery can be reduced. Therefore, the addition of the organic additive to the negative electrode material can comprehensively improve the initial efficiency, cycle and high-temperature storage life of the sodium ion battery.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a negative electrode material for a sodium ion battery, the negative electrode material for a sodium ion battery including a negative electrode active material and an organic additive;
the organic additive contains at least 2 sodium sulfonate groups, at least 1 biphenyl functional group and at least 1 azo functional group, and the benzene ring is conjugated with the azo functional group.
According to the invention, the organic additive is added into the negative electrode material for the sodium ion battery, the organic additive contains biphenyl and azo functional groups, benzene rings are conjugated with the azo functional groups, a large delocalized pi bond can be formed, the biphenyl functional groups have rigidity, the expansion of the negative electrode material in the sodium intercalation and deintercalation process can be inhibited, in addition, the sodium sulfonate group can be adsorbed on the surface of the negative electrode, the transfer of sodium ions on the surface of the negative electrode can be accelerated, and the consumption of electrolyte and active sodium ions on the surface of the negative electrode during the formation of the sodium ion battery can be reduced.
As a preferable technical scheme of the invention, the organic additive is a water-soluble azo colorant.
The water-soluble azo colorant refers to a colorant which can be dissolved in water and has azo functional groups, and is widely used in industries such as cosmetics, foods and dyes.
Preferably, the water-soluble azo-based colorant includes at least one of amaranth, sunset yellow, carmine, and allure.
The amaranth is also called acid red 27, food red 2 and cockscomb flower red, and is an organic compound with a chemical formula of C 20 H 11 N 2 Na 3 O 10 S 3 The structural formula is。
The sunset yellow has the chemical name of 6-hydroxy-5- [ (4-sulfophenyl) azo]Disodium salt of 2-naphthalenesulfonic acid having formula C 16 H 10 N 2 Na 2 O 7 S 2 The structural formula is。
The new carmine is a chemical preparation, also called acid red 18, ponceau 4R, the chemical name is 1- (4-sulfonic acid-1-naphthylazo) -2-hydroxy-6, 8-naphthalenedisulfonic acid trisodium salt, the chemical formula is C 20 H 11 N 2 Na 3 O 10 S 3 The structural formula is。
The attractive red color is brilliant red, alara red, edible red No. 40 (Japanese name), and the molecular formula is C 18 H 14 N 2 Na 2 O 8 S 2 The structural formula is。
In a preferred embodiment of the present invention, the mass fraction of the organic additive is 0.1 to 2% based on the mass of the negative electrode material, and may be, for example, 0.1%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 1.3%, 1.5%, 1.7%, 1.9%, or the like.
In the invention, if the mass fraction of the organic additive is too small, the surface of the anode active material cannot be effectively coated, and the effect cannot be exerted; if the mass fraction of the organic additive is too large, the coating is too thick on the surface of the negative electrode, which can prevent sodium ions from migrating on the surface of the negative electrode, and the energy density of the sodium ion battery can be obviously reduced.
As a preferable technical scheme of the invention, the negative electrode material for the sodium ion battery further comprises a sodium-containing inorganic salt additive.
In the invention, the sodium-containing inorganic salt additive can be attached to the surface of the negative electrode as a component of the interfacial film, and the high-temperature cycle and the storage life of the sodium ion battery can be further improved by adding the sodium-containing additive on the basis of the organic additive.
According to the invention, the organic additive belongs to a macromolecular compound, when the surface of the negative electrode material is coated, gaps exist between the formed artificial interface films, and on the basis, the sodium-containing inorganic salt additive is added, so that the inorganic salt additive has smaller molecular weight and can fill the gaps of the artificial interface film formed by the organic additive, thereby forming a denser artificial interface film, further reducing the thickness of the interface film on the surface of the sodium ion battery, shortening the transmission path of sodium ions on the surface of the negative electrode and improving the quick charge performance; in addition, the sodium-containing inorganic salt additive contains sodium ions, so that the consumption of the sodium ions on the surface of the negative electrode can be reduced, and the initial effect of the battery is further improved.
Preferably, the sodium-containing inorganic salt additive includes at least one of sodium carbonate, sodium phosphate, sodium silicate, and sodium sulfate.
In a preferred embodiment of the present invention, the sodium-containing inorganic salt additive may be 0.1 to 1% by mass, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1% by mass, based on the mass of the negative electrode material.
In the invention, if the mass fraction of the sodium-containing inorganic salt additive is too small, the surface of the anode active material cannot be effectively coated, and the effect cannot be exerted; if the mass fraction of the sodium-containing inorganic salt additive is too large, the coating on the surface of the negative electrode is too thick, so that migration of sodium ions on the surface of the negative electrode is blocked, and the energy density of the sodium ion battery is obviously reduced.
As a preferred embodiment of the present invention, the negative electrode active material includes at least one of hard carbon, soft carbon, and a soft carbon-hard carbon composite.
Preferably, the negative electrode material for sodium ion battery further comprises a conductive agent and a binder.
Preferably, the conductive agent includes at least one of carbon black, carbon nanotubes, and graphene.
Preferably, the binder includes at least one of polyvinylidene fluoride, styrene-butadiene rubber, polyacrylate, polyacrylonitrile, polyacrylic acid, sodium polyacrylate, carboxymethyl cellulose, sodium alginate, acacia, xanthan gum, and guar gum.
As a preferable technical scheme of the invention, the specific surface area of the negative electrode material for the sodium ion battery is 2-10g/m 2 For example, it may be 2g/m 2 、4g/m 2 、6g/m 2 、8g/m 2 Or 10g/m 2 Etc.
In a second aspect, the invention provides a negative electrode plate, which comprises a negative electrode current collector and a negative electrode active layer coated on the surface of the negative electrode current collector, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery in the first aspect.
As a preferable technical scheme of the invention, the negative electrode current collector is copper foil or aluminum foil.
In a preferred embodiment of the present invention, the negative electrode active layer has a thickness of 120 to 250. Mu.m, for example, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, 210 μm, 220 μm, 230 μm, 240 μm, 250 μm, or the like.
The preparation method of the negative electrode plate is not particularly limited, and exemplary, the preparation method comprises the following steps:
mixing a negative electrode active material for a sodium ion battery, an organic additive, a sodium-containing inorganic salt additive, a conductive agent, a binder and a solvent to obtain a negative electrode slurry;
and coating the negative electrode slurry on the surface of a negative electrode current collector, and drying to obtain the negative electrode plate.
In a third aspect, the present invention provides a sodium ion battery comprising a negative electrode sheet as described in the second aspect.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the organic additive is added into the negative electrode material for the sodium ion battery, so that the negative electrode material is uniformly coated on the surface of the negative electrode material to serve as an artificial interface film, and due to the existence of the artificial interface film, a layer of interface film grows on the outer layer during formation of the sodium ion battery, and finally, the side reaction on the surface of the negative electrode can be more effectively inhibited under the protection of the double-layer interface film, and the cycle performance and the high-temperature performance of the sodium ion battery are improved.
(2) In the invention, the adopted organic additive contains biphenyl and azo groups, benzene rings are conjugated with azo functional groups, so that a large delocalized pi bond can be formed, the conductivity of the surface of the negative electrode can be improved, and the direct current internal resistance of the sodium ion battery can be reduced; the biphenyl functional group has strong rigidity, can inhibit the expansion of the anode material in the sodium intercalation and deintercalation process, and can inhibit the damage of the anode interface film and the consumption of sodium ions in the circulation process; in addition, 2 sodium sulfonate groups can be firmly adsorbed on the surface of the negative electrode under the action of polar groups such as hydroxyl groups and the like on the surface of the negative electrode material, can improve the transmission of sodium ions on the surface of the negative electrode, improve the quick charge performance and can reduce the consumption of electrolyte and active sodium ions on the surface of the negative electrode during the formation of a sodium ion battery. Therefore, the organic additive is added into the anode material, so that the first effect, the fast charge cycle and the high-temperature storage life of the sodium ion battery can be comprehensively improved.
Drawings
FIG. 1 is a schematic view of an interfacial film formed when a sodium ion battery prepared from the negative electrode material for a sodium ion battery according to example 1 of the present invention is formed.
FIG. 2 is a schematic view of an interfacial film formed when a sodium ion battery prepared from the negative electrode material for a sodium ion battery according to example 9 of the present invention is formed.
FIG. 3 is a schematic view of an interfacial film formed when a sodium ion battery prepared as a negative electrode material for a sodium ion battery according to comparative example 5 of the present invention is formed.
Wherein, 1-negative electrode active material; 2-an interfacial film formed by the reaction of the electrolyte; 3-organic additive interfacial film; 4-sodium-containing inorganic salt additive interfacial film.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a negative electrode material for a sodium ion battery, which comprises a negative electrode active material, an organic additive, a sodium-containing inorganic salt additive, a conductive agent and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is amaranth, wherein the amaranth contains 3 sodium sulfonate groups, 2 biphenyl functional groups and 1 azo functional group, and a benzene ring is conjugated with the azo functional group; the sodium-containing inorganic salt additive is sodium carbonate; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 1%, the mass fraction of the sodium-containing inorganic salt additive is 0.5%, the mass fraction of the conductive agent is 1.5%, and the mass fractions of the binder carboxymethyl cellulose and styrene butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) According to the proportion, stirring and mixing hard carbon, amaranth, sodium carbonate, carbon black, carboxymethyl cellulose, styrene-butadiene rubber and a solvent to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Fig. 1 shows a schematic view of an interfacial film formed during formation of a sodium ion battery made of a negative electrode material for a sodium ion battery provided in example 1, and it is understood that an organic additive interfacial film 3 is formed on the surface of a negative electrode active material 1, and at the same time, an inorganic salt additive containing sodium is used to fill the gaps of the organic additive interfacial film 3, and an interfacial film 4 containing inorganic salt is formed, so that the interfacial film 2 generated by the reaction of the organic additive interfacial film 3, the inorganic salt additive containing sodium interfacial film 4 and an electrolyte can effectively reduce the thickness of the interfacial film on the surface of a sodium ion battery, shorten the transmission path of sodium ions on the surface of a negative electrode, and improve the quick charge performance.
Example 2
The embodiment provides a negative electrode material for a sodium ion battery, which comprises a negative electrode active material, an organic additive, a sodium-containing inorganic salt additive, a conductive agent and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is sunset yellow, wherein the sunset yellow contains 2 sodium sulfonate groups, 1 biphenyl functional group and 1 azo functional group, and a benzene ring is conjugated with the azo functional group; the sodium-containing inorganic salt additive is sodium phosphate; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 0.1%, the mass fraction of the sodium-containing inorganic salt additive is 1%, the mass fraction of the conductive agent is 1.5%, and the mass fractions of the binder carboxymethyl cellulose and styrene butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) According to the proportion, stirring and mixing hard carbon, sunset yellow, sodium phosphate, carbon black, carboxymethyl cellulose, styrene-butadiene rubber and a solvent to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Example 3
The embodiment provides a negative electrode material for a sodium ion battery, which comprises a negative electrode active material, an organic additive, a sodium-containing inorganic salt additive, a conductive agent and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is new carmine, 3 sodium sulfonate groups, 2 biphenyl functional groups and 1 azo functional group are contained in the new carmine, and a benzene ring is conjugated with the azo functional groups; the sodium-containing inorganic salt additive is sodium silicate; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 0.5%, the mass fraction of the sodium-containing inorganic salt additive is 0.8%, the mass fraction of the conductive agent is 1.5%, and the mass fractions of the binder carboxymethyl cellulose and styrene-butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) According to the proportion, stirring and mixing hard carbon, carmine, sodium silicate, carbon black, carboxymethyl cellulose, styrene-butadiene rubber and a solvent to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Example 4
The embodiment provides a negative electrode material for a sodium ion battery, which comprises a negative electrode active material, an organic additive, a sodium-containing inorganic salt additive, a conductive agent and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is allure red, wherein the allure red contains 2 sodium sulfonate groups, 1 biphenyl functional group and 1 azo functional group, and a benzene ring is conjugated with the azo functional group; the sodium-containing inorganic salt additive is sodium sulfate; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 2%, the mass fraction of the sodium-containing inorganic salt additive is 1%, the mass fraction of the conductive agent is 1.5%, and the mass fractions of the binder carboxymethyl cellulose and styrene-butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) Stirring and mixing hard carbon, allure red, sodium sulfate, carbon black, carboxymethyl cellulose and a solvent according to the proportion to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Example 5
The embodiment provides a negative electrode material for a sodium ion battery, which comprises a negative electrode active material, an organic additive, a sodium-containing inorganic salt additive, a conductive agent and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is amaranth, wherein the amaranth contains 3 sodium sulfonate groups, 2 biphenyl functional groups and 1 azo functional group, and a benzene ring is conjugated with the azo functional group; the sodium-containing inorganic salt additive is sodium carbonate; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 0.05%, the mass fraction of the sodium-containing inorganic salt additive is 0.5%, the mass fraction of the conductive agent is 1.5%, and the mass fractions of the binder carboxymethyl cellulose and styrene-butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) Stirring and mixing hard carbon, amaranth, sodium carbonate, carbon black, carboxymethyl cellulose and a solvent according to the proportion to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Example 6
The embodiment provides a negative electrode material for a sodium ion battery, which comprises a negative electrode active material, an organic additive, a sodium-containing inorganic salt additive, a conductive agent and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is amaranth, wherein the amaranth contains 3 sodium sulfonate groups, 2 biphenyl functional groups and 1 azo functional group, and a benzene ring is conjugated with the azo functional group; the sodium-containing inorganic salt additive is sodium carbonate; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 2.5%, the mass fraction of the sodium-containing inorganic salt additive is 0.5%, the mass fraction of the conductive agent is 1.5%, and the mass fractions of the binder carboxymethyl cellulose and styrene-butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) Stirring and mixing hard carbon, amaranth, sodium carbonate, carbon black, carboxymethyl cellulose and a solvent according to the proportion to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Example 7
The embodiment provides a negative electrode material for a sodium ion battery, which comprises a negative electrode active material, an organic additive, a sodium-containing inorganic salt additive, a conductive agent and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is amaranth, wherein the amaranth contains 3 sodium sulfonate groups, 2 biphenyl functional groups and 1 azo functional group, and a benzene ring is conjugated with the azo functional group; the sodium-containing inorganic salt additive is sodium carbonate; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 1%, the mass fraction of the sodium-containing inorganic salt additive is 0.05%, the mass fraction of the conductive agent is 1%, and the mass fractions of the binder carboxymethyl cellulose and styrene-butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) Stirring and mixing hard carbon, amaranth, sodium carbonate, carbon black, carboxymethyl cellulose and a solvent according to the proportion to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Example 8
The embodiment provides a negative electrode material for a sodium ion battery, which comprises a negative electrode active material, an organic additive, a sodium-containing inorganic salt additive, a conductive agent and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is amaranth, wherein the amaranth contains 3 sodium sulfonate groups, 2 biphenyl functional groups and 1 azo functional group, and a benzene ring is conjugated with the azo functional group; the sodium-containing inorganic salt additive is sodium carbonate; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 1%, the mass fraction of the sodium-containing inorganic salt additive is 1.5%, the mass fraction of the conductive agent is 1.5%, and the mass fractions of the binder carboxymethyl cellulose and styrene butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) Stirring and mixing hard carbon, amaranth, sodium carbonate, carbon black, carboxymethyl cellulose and a solvent according to the proportion to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Example 9
The present embodiment provides a negative electrode material for a sodium ion battery including a negative electrode active material, an organic additive, a conductive agent, and a binder;
the negative electrode active material is hard carbon with a ratio of 6g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The organic additive is amaranth, wherein the amaranth contains 3 sodium sulfonate groups, 2 biphenyl functional groups and 1 azo functional group, and a benzene ring is conjugated with the azo functional group; the conductive agent is carbon black, and the binder is a mixture of carboxymethyl cellulose and styrene-butadiene rubber;
based on the mass of the anode material, the mass fraction of the organic additive is 1%, the mass fraction of the conductive agent is 1.5%, and the mass fractions of the binder carboxymethyl cellulose and the styrene-butadiene rubber are respectively 1.5% and 3%.
The embodiment also provides a negative electrode plate, which comprises a negative electrode current collector copper foil and a negative electrode active layer coated on the surface of the copper foil, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery;
wherein the thickness of the anode active layer was 180. Mu.m.
The embodiment also provides a preparation method of the negative electrode plate, which comprises the following steps:
(1) Stirring and mixing hard carbon, amaranth, carbon black, carboxymethyl cellulose and a solvent according to the proportion to obtain negative electrode slurry;
wherein the solvent is deionized water;
(2) And uniformly coating the negative electrode slurry on the surface of a negative electrode current collector copper foil by using a coating scraper, carrying out cold pressing, trimming, cutting and slitting, drying for 4 hours under the vacuum condition of 110 ℃, and welding the electrode lugs to prepare the negative electrode plate of the sodium ion battery meeting the requirements.
Fig. 2 shows a schematic diagram of an interfacial film formed during formation of a sodium ion battery made of a negative electrode material for a sodium ion battery according to example 9, and it is known that an organic additive interfacial film 3 is formed on the surface of a negative electrode active material 1, and the interfacial film 2 generated by combining with an electrolyte reaction can reduce the internal resistance of the battery, and can reduce the consumption of active sodium ions by the electrolyte during formation, thereby improving the initial efficiency.
Comparative example 1
This comparative example differs from example 1 only in that the organic additive amaranth was replaced with saffron orange G.
Comparative example 2
This comparative example differs from example 1 only in that the organic additive amaranth was replaced with sudan-1.
Comparative example 3
This comparative example differs from example 1 only in that the organic additive amaranth was replaced with 4-hydroxyazobenzene-4' -sulfonyl sodium salt.
Comparative example 4
This comparative example differs from example 1 only in that the organic additive amaranth was replaced by sodium 1,3, 6-naphthalene trisulphonate.
Comparative example 5
This comparative example differs from example 1 only in that the negative electrode material for sodium ion batteries does not contain amaranth as an organic additive.
Fig. 3 is a schematic view showing an interfacial film formed during formation of a sodium ion battery made of the negative electrode material for a sodium ion battery provided in comparative example 5, and it is understood that only the interfacial film 2 generated by the reaction of the electrolyte is formed on the surface of the negative electrode active material 1, and the interfacial film is thicker, which is not beneficial to shortening the transmission path of sodium ions on the surface of the negative electrode and reducing the consumption of active sodium ions by the electrolyte during formation.
Performance testing
The negative electrode piece, the positive electrode piece, the electrolyte and the diaphragm provided by the embodiment and the comparative example are made into a sodium ion battery, and the specific steps include:
(1) Preparing a positive electrode plate:
positive electrode active material sodium nickel iron manganese oxide NaNi 0.3 Fe 0.4 Mn 0.3 O 2 The mass ratio of the binder (polyvinylidene fluoride) to the conductive agent (conductive carbon black) is fixed to be 96:2:2, and the positive electrode material sodium nickel iron manganese oxide, the binder, the conductive agent, the additive A and the additive B are mixed according to the respective proportion requirements, and are stirred after being added with N-methyl pyrrolidone (NMP) to prepare positive electrode slurry;
uniformly coating the anode slurry on an aluminum foil, airing the coated aluminum foil at room temperature, and transferring the aluminum foil to a 120 ℃ oven for drying for 1h; and then drying at 85 ℃, cold pressing, trimming, cutting pieces and splitting, drying for 4 hours at 85 ℃ under vacuum, and welding the tab to prepare the positive pole piece of the sodium ion battery meeting the requirements.
Wherein the thickness of the positive electrode active layer was 130. Mu.m.
(2) Preparing an electrolyte:
firstly, in a glove box, slowly adding sodium hexafluorophosphate into a mixed solution of solvent Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC), and after the temperature in a container is reduced to room temperature, adding 1% fluoroethylene carbonate (FEC) additive. The mass ratio of EC, DMC and EMC in the electrolyte is EC: DMC: emc=1:1:1, the mass fraction of sodium hexafluorophosphate in the electrolyte was 14%.
(3) Preparation of sodium ion battery:
and winding the corresponding positive pole piece, negative pole piece and isolating film (PE film+3um ceramic coating) into a bare cell, then filling the bare cell into an aluminum plastic film, baking at 90 ℃ to remove water, filling electrolyte, sealing, standing, hot-cold pressing, forming, exhausting, separating volume and the like to obtain the sodium ion battery.
The sodium ion battery is subjected to electrochemical performance tests, including initial efficiency, cycle performance and high-temperature storage performance.
First effect (first charge-discharge efficiency) test:
the first efficiency test flow is included in the sodium ion battery formation and capacity separation flow. Standing the sodium ion battery at 25deg.C for 30 min, constant-current charging to 4.0V at 0.3C rate, constant-voltage charging to 0.05C at 4.0V, and recording the total capacity of the battery as C 0 The method comprises the steps of carrying out a first treatment on the surface of the Then standing for 30 minutes, then discharging to 1.5V at constant current with 0.3C multiplying power, and recording the total capacity of discharged to be D 0 。
Sodium ion battery initial effect (%) =d 0 /C 0 ×100%。
And (3) testing the quick charge cycle performance:
standing the sodium ion battery at 25 ℃ for 30 minutes, then charging to 4.0V at constant current with 3C multiplying power, then charging to 0.05C at constant voltage with 4.0V, standing for 5 minutes, then discharging to 1.5V with 1C multiplying power, wherein the discharge capacity is the first discharge capacity C of the sodium ion battery 1 The method comprises the steps of carrying out a first treatment on the surface of the Then 500 charge-discharge cycles are carried out, and the discharge capacity of 500 th cycle is recorded as C 500 。
Capacity retention (%) =c after 500 cycles of the sodium ion battery 500 /C 1 。
High temperature storage test:
firstly, standing the sodium ion battery at 25 ℃ for 30 minutes; charging to 4.0V at a constant current of 0.5C, further charging to a current of 0.5C at a constant voltage of 4.0V; then, the sodium ion battery was discharged at a constant current of 0.5C for 1.5V, at which time the discharge capacity was recorded as C 0s The method comprises the steps of carrying out a first treatment on the surface of the Charging to 4.0V with constant current of 0.5C, and further charging to 0.5C with constant voltage of 4.0V; finally, the volume of the battery is tested by a drainage method, wherein the volume is V before storage 0 . Then the sodium ion battery is stored for 30 days at 60 ℃, after the storage is finished, the sodium ion secondary battery is placed in an environment of 25 ℃, and the volume of the battery is tested by adopting a drainage method, wherein the volume is V after the storage 30 . Then discharging the sodium ion battery to 1.5V at a constant current of 0.5C, charging the sodium ion secondary battery to 4.0V at a constant current of 0.5C, further charging the sodium ion secondary battery to 0.5C at a constant voltage of 4.0V, and discharging the sodium ion secondary battery to 1.5V at a constant current of 0.5C, wherein the discharge capacity is marked as C 30s 。
Storage capacity recovery rate (%) =c after 30 days of sodium ion storage 30S /C 0s ；
Volume expansion rate (%) = (V) of sodium ion battery after 30 days storage 30 -V 0 )/V 0 。
The test results are shown in Table 1.
TABLE 1
Analysis:
as can be seen from the data of the above examples and comparative examples, the organic additive is added to the negative electrode material for sodium ion battery, the organic additive is uniformly coated on the surface of the negative electrode active material, which is equivalent to coating a layer of artificial interfacial film on the surface of the negative electrode active material, and due to the existence of the artificial interfacial film, a thin interfacial film grows on the outer layer during formation of the sodium ion battery, and finally, the side reaction on the surface of the negative electrode can be more effectively inhibited under the protection of the double-layer interfacial film, and the cycle performance and the high-temperature performance of the sodium ion battery are improved.
The sodium ion battery prepared by the invention has a thinner interface film, can reduce the internal resistance of the battery, and can reduce the consumption of active sodium ions by electrolyte during formation, thereby improving the first effect. Therefore, the first effect, the fast charge cycle and the high-temperature storage life of the sodium ion battery can be comprehensively improved by adding the organic additive into the anode material.
In addition, the inorganic salt additive is added on the basis of adding the organic additive into the negative electrode, so that the artificial interface film can be further modified, the compactness and the thermal stability of the interface film are improved, the consumption of active sodium ions can be reduced, and the first effect, the quick charge cycle life and the high-temperature storage life of the sodium ion battery are further improved.
As is clear from comparison of the data results of examples 1 and examples 5 to 6, if the amount of the organic additive is too small, the improvement of the overall performance of the sodium ion battery is not obvious, mainly because the organic additive acts on the surface of the negative electrode, and the content of the organic additive is too small to form a uniform and compact artificial interface film on the surface of the negative electrode, so that the function of the artificial interface film cannot be exerted; if the organic additive is used in an excessive amount, it may cause an artificial interfacial film formed on the surface of the negative electrode to be too thick, and the transport of sodium ions on the surface of the negative electrode may be hindered, resulting in deterioration of the rapid charge cycle performance.
As is evident from comparison of the data results of examples 1 and examples 7 to 8, too little amount of the sodium-containing inorganic salt additive results in an ineffective filling of the gap of the artificial interfacial film formed by the organic additive at the negative electrode, and no significant improvement in the performance of the sodium-ion battery; if the dosage of the sodium-containing inorganic salt additive is too large, the thickness of the interfacial film on the surface of the negative electrode is not reduced, but the thickness is increased, so that sodium ions are difficult to transport on the surface of the negative electrode, and the quick charge cycle performance is obviously deteriorated.
As is clear from comparison of the data obtained in example 1 and example 9, if the sodium-containing inorganic salt additive is not added, the gap between the organic additive and the artificial interface film formed on the negative electrode cannot be filled, the interface film is not dense enough, and the thermal stability of the interface film is lowered to some extent, resulting in a decrease in the overall performance.
As is clear from comparison of the data of example 1 and comparative examples 1-2, if the organic additive used contains only one sodium sulfonate group, the sodium ion transport capacity will be reduced, the consumption of active sodium ions will be increased, and the overall performance of the sodium ion battery will be reduced; if the organic additive does not contain sodium sulfonate groups, the additive cannot be uniformly dispersed in the negative electrode slurry due to low solubility in water in the process of preparing the negative electrode plate, cannot be uniformly coated on the surface of the negative electrode, and the sodium ion transmission capacity is obviously reduced, the consumption of active sodium ions is increased, and the comprehensive performance of the sodium ion battery is obviously reduced.
As is clear from comparison of the data results of example 1 and comparative examples 3 to 4, if the organic additive used does not contain biphenyl functional groups, the effect of the organic additive in inhibiting the expansion of the anode material is reduced, the conductivity is also reduced, and various performances of the sodium ion battery are reduced; if the adopted organic additive does not contain azo functional groups, the large delocalized pi bond bridged by the azo groups of the organic additive can be broken, the conductivity can be reduced, and the first effect and the cycle performance can be reduced.
As is clear from comparison of the data of example 1 and comparative example 5, when the negative electrode material for sodium ion battery contains no organic additive, an artificial interfacial film excellent in both conductivity and compactness cannot be formed on the negative electrode surface, and the various properties cannot be improved.
The applicant states that the invention is illustrated by the above examples, but the invention is not limited to the above process steps, i.e. it does not mean that the invention must be carried out in dependence of the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A negative electrode material for a sodium ion battery, characterized in that the negative electrode material for a sodium ion battery comprises a negative electrode active material and an organic additive;
the organic additive contains at least 2 sodium sulfonate groups, at least 1 biphenyl functional group and at least 1 azo functional group, and the benzene ring is conjugated with the azo functional group.
2. The negative electrode material for sodium ion battery according to claim 1, wherein the organic additive is a water-soluble azo-based colorant;
the water-soluble azo colorant comprises at least one of amaranth, sunset yellow, carmine and allure.
3. The negative electrode material for sodium ion battery according to claim 1, wherein the mass fraction of the organic additive is 0.1 to 2% based on the mass of the negative electrode material.
4. The negative electrode material for sodium-ion battery according to claim 1, wherein the negative electrode material for sodium-ion battery further comprises a sodium-containing inorganic salt additive;
the sodium-containing inorganic salt additive includes at least one of sodium carbonate, sodium phosphate, sodium silicate, and sodium sulfate.
5. The negative electrode material for sodium-ion batteries according to claim 4, wherein the sodium-containing inorganic salt additive is present in an amount of 0.1 to 1% by mass based on the mass of the negative electrode material.
6. The anode material for a sodium-ion battery according to claim 1, wherein the anode active material includes at least one of hard carbon, soft carbon, and a soft carbon-hard carbon composite;
the negative electrode material for the sodium ion battery also comprises a conductive agent and a binder;
the conductive agent comprises at least one of carbon black, carbon nanotubes and graphene;
the binder comprises at least one of polyvinylidene fluoride, styrene-butadiene rubber, polyacrylate, polyacrylonitrile, polyacrylic acid, sodium polyacrylate, carboxymethyl cellulose, sodium alginate, acacia, xanthan gum and guar gum.
7. The negative electrode material for sodium-ion battery according to claim 1, wherein the specific surface area of the negative electrode material for sodium-ion battery is 2-10g/m 2 。
8. The negative electrode plate is characterized by comprising a negative electrode current collector and a negative electrode active layer coated on the surface of the negative electrode current collector, wherein the negative electrode active layer is prepared from the negative electrode material for the sodium ion battery according to any one of claims 1-7.
9. The negative electrode tab of claim 8, wherein the negative electrode active layer has a thickness of 120-250 μm.
10. A sodium ion battery comprising the negative electrode tab of claim 8 or 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004063123A (en) * | 2002-07-25 | 2004-02-26 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2007073232A (en) * | 2005-09-05 | 2007-03-22 | Japan Carlit Co Ltd:The | Separator for fuel cell and method of manufacturing same |
| CN107910194A (en) * | 2017-11-23 | 2018-04-13 | 福州大学 | A kind of preparation method of nanometer fibrous amaranth doped polyaniline electrode material |
| CN110048121A (en) * | 2019-03-27 | 2019-07-23 | 广东萱嘉医品健康科技有限公司 | A kind of negative electrode material containing azo organic lithium salt, cathode pole piece, lithium battery and preparation method thereof |
| WO2023109708A1 (en) * | 2021-12-15 | 2023-06-22 | 深圳先进技术研究院 | Sodium-based dual-ion battery and preparation method therefor |
| CN116605867A (en) * | 2023-05-24 | 2023-08-18 | 福建省鑫森炭业股份有限公司 | Negative electrode material of sodium ion battery and preparation method and application thereof |
-
2023
- 2023-11-02 CN CN202311445666.3A patent/CN117199326B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004063123A (en) * | 2002-07-25 | 2004-02-26 | Japan Storage Battery Co Ltd | Nonaqueous electrolyte secondary battery |
| JP2007073232A (en) * | 2005-09-05 | 2007-03-22 | Japan Carlit Co Ltd:The | Separator for fuel cell and method of manufacturing same |
| CN107910194A (en) * | 2017-11-23 | 2018-04-13 | 福州大学 | A kind of preparation method of nanometer fibrous amaranth doped polyaniline electrode material |
| CN110048121A (en) * | 2019-03-27 | 2019-07-23 | 广东萱嘉医品健康科技有限公司 | A kind of negative electrode material containing azo organic lithium salt, cathode pole piece, lithium battery and preparation method thereof |
| WO2023109708A1 (en) * | 2021-12-15 | 2023-06-22 | 深圳先进技术研究院 | Sodium-based dual-ion battery and preparation method therefor |
| CN116605867A (en) * | 2023-05-24 | 2023-08-18 | 福建省鑫森炭业股份有限公司 | Negative electrode material of sodium ion battery and preparation method and application thereof |
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