CN115679122B - Electrode with composite structure and manufacturing method and application thereof - Google Patents
Electrode with composite structure and manufacturing method and application thereof Download PDFInfo
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- CN115679122B CN115679122B CN202211474457.7A CN202211474457A CN115679122B CN 115679122 B CN115679122 B CN 115679122B CN 202211474457 A CN202211474457 A CN 202211474457A CN 115679122 B CN115679122 B CN 115679122B
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- 239000002131 composite material Substances 0.000 title claims abstract description 123
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 146
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 145
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 92
- 238000003860 storage Methods 0.000 claims abstract description 68
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims description 77
- 238000000605 extraction Methods 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 229910013716 LiNi Inorganic materials 0.000 claims description 7
- 238000005056 compaction Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 238000007788 roughening Methods 0.000 claims description 7
- 239000011232 storage material Substances 0.000 claims description 7
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 claims description 6
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 6
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 229910021385 hard carbon Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 230000003746 surface roughness Effects 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000003011 anion exchange membrane Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 4
- 229910018871 CoO 2 Inorganic materials 0.000 claims description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005087 graphitization Methods 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910012820 LiCoO Inorganic materials 0.000 claims description 2
- 229910010710 LiFePO Inorganic materials 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 2
- 238000012423 maintenance Methods 0.000 abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 38
- 229910052742 iron Inorganic materials 0.000 description 19
- 239000013535 sea water Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- 239000011572 manganese Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- 229910001425 magnesium ion Inorganic materials 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 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 description 3
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010981 drying operation Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 229910020717 Li0.33La0.56TiO3 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
Abstract
An electrode with a composite structure, a manufacturing method and application thereof, wherein the electrode with the composite structure comprises a lithium storage layer and a selectively permeable layer coated on the surface of the lithium storage layer; the invention also comprises a manufacturing method and application of the electrode with the composite structure. The electrode with the composite structure has high adsorption capacity to lithium, high lithium ion storage capacity and high cycle stability, and the equipment cost for manufacturing and applying the electrode with the composite structure is low. The composite electrode has low cost and low total cost; the maintenance is convenient, and after the surface coating is damaged, the surface coating can be repaired by adding the coating.
Description
Technical Field
The invention relates to an electrode and a manufacturing method and application thereof, in particular to a composite structure electrode and a manufacturing method and application thereof.
Background
The seawater contains 0.17ppm of lithium and a large amount of sodium, potassium, calcium and magnesium ions, so that the difficulty in extracting lithium is high. The traditional method mainly uses a solvent extraction method and an adsorbent method in the research of extracting lithium from seawater, and the two methods have high cost and only stay in a laboratory stage. The development of new lithium extraction technology is imperative, and electrochemical lithium extraction has certain selectivity, so that the method becomes a current research hotspot.
Kanoh et al in 1993 proposed the use of lambda-MnO 2 as a working electrode for electrochemical lithium extraction. Lithium ion in LiMn 2 O 4 The reaction equation of extracting and inserting lithium in the electrode material and the inserting lithium are shown in the formulas (1) to (3):
and (3) a negative electrode: liMn 2 O 4 = Li 0.5 Mn 2 O 4 + 0.5Li + + 0.5e − （1)
Li 0.5 Mn 2 O 4 = 2λ-MnO 2 + 0.5Li + + 0.5e − (2)
And (3) a positive electrode: 2 lambda-MnO 2 + Li + + e − =LiMn 2 O 4 (3)
The method adopts LiMn 2 O 4 The electrode, the subsequent problems of dissolution loss and poor conductivity of manganese, and in addition, the electrode material is corroded in seawater or brine.
In lithium ion aqueous solution lithium intercalation behavior research, dan Xiaoqian proposes the idea of extracting lithium from an aqueous solution by using a lithium iron phosphate electrode for the first time. CN102049238A is an ion sieve for selectively extracting lithium and application thereof, and discloses a method for preparing a lithium iron phosphate ion sieve and application thereof. CN110777390a discloses an electrochemical method for self-driven lithium extraction based on a rocking chair type structure electrode system, wherein a lithium-poor state and lithium-rich state positive electrode material is assembled into a working electrode for electrochemical lithium extraction.
In the above disclosed methods, the lithium ion battery positive electrode material is used as the active material for adsorption and storage of lithium. However, the anode materials of lithium ion batteries, such as lithium iron phosphate, ternary lithium manganate and lithium manganate, which are widely used at present have the problem of low electronic conductivity and low ionic conductivity. Resulting in the fact that only thin electrodes can be used in the manufacture of the electrode. In addition, the positive electrode material of the lithium ion battery generally contains very low lithium, for example, the lithium iron phosphate is saturated, and the lithium content is up to 4.4%.
The factors determine that the adsorption capacity of the lithium ion battery anode material serving as an electrochemical lithium extraction system is low, and the best lithium iron phosphate lithium extraction system is prepared on the market, wherein the adsorption capacity of lithium is only 30mg/g. In practice, adsorption saturation occurs very quickly. Frequent intercalation and deintercalation operations lead to dissolution loss and falling of the lithium-extracting active material. The electrode has high maintenance cost and low lithium extraction efficiency.
In summary, the general problems of electrochemical lithium extraction are:
(1) The electron conductivity is low. LiCoO 2 、LiMn 2 O 4 And LiFePO 4 Are poor electronic conductors with conductivities of 10 respectively -4 、10 -6 And 10 -9 S/cm. The electrode can only be made into a thin electrode, and the total lithium storage capacity is low.
(2) The lithium storage unit capacity is low. LiMn of lithium extraction working electrode reported in prior art 2 O 4 And LiFePO 4 And the theoretical storage capacity is 38.6mg/g and 44.3mg/g respectively. The theoretical storage lithium capacity is low.
(3) The cyclic stability is poor. Li (Li) 1-x After repeated circulation, mn2O4/LiMn2O4 is easy to cause disproportionation reaction of trivalent manganese ions, so that the dissolution loss of manganese is caused, and the circulation performance is reduced. Li (Li) 1-x The capacity also decays during FePO4/LiFePO4 recycling.
(4) The equipment cost is high. The existing lithium extraction electrode has low electronic conductivity and low lithium ion storage capacity. With the same lithium salt yield, more equipment is required and the investment cost is high.
Disclosure of Invention
The invention aims to solve the technical problems and overcome the defects in the prior art, and provides an electrode with a composite structure, which has high adsorption capacity and good cycle stability, and a manufacturing method and application thereof.
The technical scheme adopted for solving the technical problems is as follows: an electrode with a composite structure comprises a lithium storage layer and a selectively permeable layer coated on the surface of the lithium storage layer;
the lithium storage layer is made of one or more of carbon material, silicon-carbon material and silicon-oxygen material;
the selectively permeable layer is made of lithium ion positive electrode material and titaniumLithium acid material, lithium lanthanum titanium oxide, LATP material, LAGP material, liCl 2Al (OH) 3 ·nH 2 O material, garnet-structured Li 5+x La 3 M 2 O 12 One or more than two materials; the Li is 5+x La 3 M 2 O 12 M in (2) represents one or more of Nb, ta and Zr.
Preferably, the electrode of the composite structure further comprises a current collector.
Preferably, the lithium storage layer is covered on the surface of the current collector and is positioned between the current collector and the selectively permeable layer.
Preferably, the thickness of the current collector is 1-5 mm; the current collector can be in a sheet shape, a rod shape and other conventional shapes, and the current collector can be provided with a through hole; the current collector may be a commercially available product directly or a metal material such as titanium, steel, copper, or aluminum may be used as the current collector.
Preferably, the thickness of one side of the lithium storage layer is 0.1-50 mm, and more preferably 5-25 mm.
Preferably, the thickness of one side of the selectively permeable layer is 5-200 um, more preferably 10-100 um.
Preferably, the carbon material is one or more of graphite, hard carbon, soft carbon and graphene.
Preferably, the material of the lithium storage layer is that the fixed carbon content is more than or equal to 99.9%; the granularity of D50 is 5.0-30.0 um, D max Less than or equal to 70um; graphite with graphitization degree more than or equal to 90%; the lithium storage capacity of the material is more than or equal to 80mg/g, and the recycling frequency of the material serving as an electrode can reach 4000 times.
Preferably, the material of the lithium storage layer is that the fixed carbon content is more than or equal to 99%; the granularity of D50 is 5.0-10.0 um, D max Less than or equal to 30um; the compacted density of the powder is more than or equal to 1.0g/cm 3 A hard carbon negative electrode of (a); the lithium storage capacity of the material is more than or equal to 100mg/g, and the cyclic utilization times of the material serving as an electrode is more than 5000 times.
Preferably, the material of the lithium storage layer is that the SiO content is more than or equal to 20 percent and the C content is less than or equal to 80 percent; d50 is 10-20 um, D max Less than or equal to 40um; the compaction density is more than or equal to 1.0g/cm 3 Silicon oxide material SiO; the lithium storage capacity of the material is more than or equal to 120mg/g, and the cyclic utilization times of the material serving as an electrode is more than 1000 times.
Preferably, the material of the lithium storage layer is Si with the content of more than or equal to 2 percent and carbon with the content of less than or equal to 98 percent; d50 is 10-20 um, D max Not more than 32um; the compaction density is more than or equal to 1.0g/cm 3 Silicon carbon material SiC of (a); the lithium storage capacity of the material is more than or equal to 130mg/g, and the cyclic utilization times of the material serving as an electrode is more than 2000 times.
Preferably, the material of the selectively permeable layer is LiFePO 4 、LiMn 2 O 4 、LiCoO 2 、LiNi 1-a-b Co a Mn b O 2 、Li 4 Ti 5 O 12 、Li 7 Ti 5 O 12 Wherein 0 is<a≤1，0<b is less than or equal to 1; the above materials can be purchased directly.
Preferably, the material of the selectively permeable layer is LiFePO with Li content of 4.3+ -0.3%, fe content of 34.0+ -2.0%, P content of 19.5+ -1.5%, electron microscope average particle diameter of less than 100nm, and secondary agglomerate particle of less than 30um 4 。
Preferably, the material of the selectively permeable layer has Mn content of 58+ -2.0% and Li content of 4.2+ -0.4%; d50 is 6-14 um, D max LiMn less than or equal to 100um 2 O 4 。
Preferably, the material of the selectively permeable layer is Li content 7.0+ -0.5%, D50 is 4-25 um, D max LiCoO less than or equal to 70um 2 。
Preferably, the material of the selectively permeable layer is Li content 7.0+ -0.5%, D50 is 4-25 um, D max LiNi less than or equal to 70um 1-a-b Co a Mn b O 2 Wherein 0 is<a≤1，0<b≤1。
Preferably, the Ti content of the material of the selectively permeable layer is more than or equal to 45%, the Li content is 6.0+/-1.0%, and the D50 is 0.5-10 um of Li 4 Ti 5 O 12 。
Preferably, the material of the selectively permeable layer is Li 1-c FePO 4 、Li 1-d Mn 2 O 4 、Li 1-e CoO 2 、Li 1-f Ni 1-g- h Co g Mn h O 2 、Li 7-i Ti 5 O 12 Wherein 0 is<c≤1，0<d≤1，0<e≤1，0<f≤1，0<g≤1，0<h≤1，0<i is less than or equal to 4. The above five materials are respectively LiFePO 4 、LiMn 2 O 4 、LiCoO 2 、LiNi 1-g-h Co g Mn h O 2 、Li 7 Ti 5 O 12 Lithium deficient compounds of (a); can directly purchase or purchase LiFePO 4 、LiMn 2 O 4 、LiCoO 2 、LiNi 1-g-h Co g Mn h O 2 、Li 7 Ti 5 O 12 Obtained by conventional acid treatment or electrochemical methods.
Preferably, the material of the selectively permeable layer is Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 。Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Is LATP material, li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Is LAGP material; can be purchased directly or as Li 2 CO 3 ，Al 2 O 3 ，NH 4 H 2 PO 4 ，TiO 2 Or GeO 2 The raw materials are synthesized by adopting a high-temperature solid phase method.
Preferably, the material of the selectively permeable layer is Li 7 La 3 Zr 2 O 12 . The material is garnet-structured lithium lanthanum zirconium oxide, called LLZO for short; can be directly purchased or prepared by taking a lithium source, a lanthanum source, a zirconium source and a titanium source as raw materials through a solid phase method or a sol-gel method.
Preferably, the material of the selectively permeable layer is Li 3j La (2/3)-j TiO 3 Wherein 0 is<j<0.16. The material is lithium lanthanum titanium oxide, called LLTO for short; can be purchased directly or in the form of TiO 2 ，Li 2 CO 3 ，La 2 O 3 Is obtained by roasting the raw materials at high temperature.
Preferably, the material of the selectively permeable layer is LiCl 2Al (OH) 3 ·nH 2 O. The material can be directly purchased or passed through LiCl or AlCl 3 Is obtained by reaction with alkali.
Preferably, the saidThe material of the selectively permeable layer is LiFePO 4 、LiMn 2 O 4 、LiCoO 2 、LiNi 1-a-b Co a Mn b O 2 、Li 4 Ti 5 O 12 、Li 7 Ti 5 O 12 、Li 1-c FePO 4 、Li 1-d Mn 2 O 4 、Li 1-e CoO 2 、Li 1-f Ni 1-g- h Co g Mn h O 2 、Li 7-i Ti 5 O 12 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 7 La 3 Zr 2 O 12 、Li 3j La (2/3)- j TiO 3 、LiCl·2Al(OH) 3 ·nH 2 Two or more of O, 0<a≤1，0<b≤1，0<c≤1，0<d≤1，0<e≤1，0<f≤1，0<g≤1，0<h≤1，0<i≤4，0<j<0.16。
Preferably, the selectively permeable layer has a double layer or a multilayer structure.
More preferably, the selectively permeable layer is an inner layer LiFePO 4 Double layer structure of outer layer lithium lanthanum titanium oxide.
More preferably, the selectively permeable layer is an inner layer LiFePO 4 Outer LiCl 2Al (OH) 3 ·nH 2 O double layer structure.
The manufacturing method of the electrode with the composite structure comprises the following steps:
(1) Mixing the lithium ion storage material and the binder uniformly to form slurry, coating the slurry on a current collector, rolling or extrusion molding, and drying to obtain a pole piece or pole rod containing a lithium storage layer; (for coating methods, reference is made to lithium ion batteries, guo Bing, et al 2005.8, university of middle and south Press, P257-258)
(2) Carrying out surface roughening treatment on the pole piece or pole rod containing the lithium storage layer;
(3) Mixing the lithium ion selective permeation material and the binder uniformly to obtain slurry, coating the slurry on a pole piece or pole rod of the lithium storage layer with the surface roughened, and drying to obtain the electrode with the composite structure; (for a method for producing a slurry, reference is made to lithium ion batteries, guo Bing, et al, 2005.8, university of middle and south Press, P257-258)
In the step (3), the coating times are one or more than two times; when the coating is performed twice or more, the next coating is performed after the previous coating is completely dried.
Preferably, the drying temperature is 80-600 ℃.
Preferably, in the step (1), the pressure of rolling or extrusion molding is 0.1-5 MPa.
Preferably, in the step (2), the surface roughening treatment is performed so that the surface roughness Ra value is 20 to 200 μm.
Preferably, in the step (3), the coating times are 3-30 times; the surface of the manufactured composite electrode has no cracks and leakage points due to multiple coating.
The application of the electrode with the composite structure takes the electrode with the composite structure as an anode and metal as a cathode to form an electrochemical device; introducing lithium-containing liquid, and extracting lithium by metal dissolution and self-discharge; the composite electrode of the positive electrode obtains electrons; lithium ions are gradually adsorbed on the electrode of the composite structure; stopping discharging after the metal is dissolved, and continuously and automatically extracting lithium by replacing the metal sheet; the metal may be a metal capable of dissolving self-discharge in a lithium-containing liquid under such conditions as: iron, aluminum, zinc, manganese.
Or the electrode of the composite structure is taken as a cathode, and the metal is taken as an anode to form an electrochemical device; and introducing lithium-containing liquid, extracting lithium at constant pressure, and gradually adsorbing lithium ions on the electrode of the composite structure. Common lithium-containing liquids include seawater, salt lake water, and the like.
Preferably, the constant voltage lithium extraction voltage is 0-2V.
Preferably, constant voltage lithium extraction is stopped when the electrode adsorption saturation or current drops below 0.05 mA.
The reaction of the composite electrode when the composite electrode is adsorbed in the lithium-containing liquid is (taking an electrode pair consisting of a carbon negative electrode and an iron sheet as an example):
2C +2 xLi + +2 xe- = 2Li x C
xFe - 2xe - = xFe 2+
and (3) the iron releases electrons, and C obtains electrons, so that lithium ions are transferred from the lithium-containing solution to crystal lattices and crystal boundaries of the lithium storage layer through the surface selective permeation layer.
Preferably, in the application of the electrode with the composite structure, the method for releasing lithium ions in the electrode with the composite structure adsorbed with lithium ions into the extracting solution is as follows:
method A: fe with the electrode of the composite structure absorbing lithium ions as an anode 2+ The electrode is used as a cathode to form an electrochemical device, the electrolyte is used as an extracting solution, and lithium ions are released into the electrolyte by electrifying.
After the composite electrode is adsorbed and saturated, the composite electrode and Fe are taken out 2+ The iron electrode is composed of a battery, and the reaction of electrification is as follows:
2Li x C=2C +2 xLi + + 2xe-
xFe 2+ +2xe - = xFe
lithium ions are transferred from the adsorption saturated composite electrode to the extraction solution.
Preferably, in the application of the electrode with the composite structure, the method for releasing lithium ions in the electrode with the composite structure adsorbed with lithium ions into the extracting solution is as follows:
method B: the electrode of the composite structure is used as a cathode, the electrode of the composite structure absorbing lithium ions is used as an anode, an anion exchange membrane is used for separating two chambers to form an electrochemical device, lithium-containing liquid is introduced into the cathode chamber, electrolyte serving as extracting solution is arranged in the anode chamber, lithium is extracted at constant pressure, and lithium ions enter the electrolyte.
Preferably, the electrolyte is a sodium chloride solution, and the molar concentration of chloride ions in the electrolyte is the same as the total molar concentration of anions in the lithium-containing solution.
Preferably, the content of chloride ions in the electrolyte is 10-100 g/l.
Preferably, the constant voltage lithium extraction voltage is 0-2V.
Preferably, constant voltage lithium extraction is stopped when the electrode adsorption saturation or current drops below 0.05 mA.
Anion exchange membranes are commercially available, such as Versogen brand membranes in the United states, or domestic anion membranes, such as GCAM series anion membrane products of national origin technology. Monovalent anion exchange membranes can also be selected, but at a higher cost.
The reaction of the composite electrode in method B is as follows:
adsorption saturated composite electrode releases lithium ion reaction formula:
Li x C = C + xLi + + xe-
novel composite electrode adsorption lithium ion reaction formula:
C + xLi + + xe - =Li x C
the lithium ions in the lithium-containing liquid are transferred to the electrode with the new composite structure, and the lithium ions in the electrode with the composite structure, which absorbs the lithium ions, are transferred to the extracting liquid.
The composite electrode consists of multiple layers, wherein the inner layer is mainly made of active materials for storing lithium ions, and the active materials are mainly carbon cathodes and silicon-carbon cathodes. The material has the characteristics of high capacity of storing lithium ions, high electronic conductivity, high cycle times and low cost, and can be made into thick electrodes, even 50mm thick. The lithium storage layer manufactured in this way can greatly improve the total amount of stored lithium ions; the selectively permeable layer adopted as the outer layer can selectively permeate Li + Isolate most of Na + 、K + 、Mg 2+ The plasma cations and anions, meanwhile, the plasma is required to have certain electronic insulation property, so that self-discharge and electric leakage are reduced, and energy consumption is reduced; as a result of studies, the inventors have found that the following classes of materials are suitable for use in making selectively permeable layers, such as: the common lithium ion battery anode material can selectively penetrate lithium ions and has the characteristic of low electronic conductivity; one of the components in the solid electrolyte, inorganic lithium ion conductor, such as LLTO and LLZO oxide, has vacancies on the structure surface, can selectively pass lithium ions, and has a lithium ion conductivity of 10 -3 ~10 -6 S/cm, as a component of the electrolyte, both LLTO and LLZO are extremely low in electron conductivity; another material is an aluminum salt adsorbentThe manganese ion sieve, the titanium ion sieve, the lithium iron phosphate ion sieve and the lithium cobalt oxide ion sieve can selectively adsorb lithium ions and can also be used for coating of a composite electrode.
The invention has the beneficial effects that:
(1) The electrode with the composite structure has high adsorption capacity to lithium, high lithium ion storage capacity and high cycle stability, and the equipment cost for manufacturing and applying the electrode with the composite structure is low; the electron conductivity of the electrode of the method is as high as 6.5 multiplied by 10 -2 s/cm, the storage capacity of lithium ions is up to 80mg/g or more, each electrode for storing lithium ions can be made into a thick electrode, and the storage capacity is large; the cycle life is up to 5000 times;
(2) The composite electrode has low cost and low total cost; the maintenance is convenient, and after the surface coating is damaged, the surface coating can be repaired by adding the coating.
Detailed Description
The invention is further illustrated by the following examples.
The starting materials used in the examples of the present invention were all obtained by conventional commercial means.
Example 1
The electrode of the composite structure of this embodiment is composed of three parts, the innermost part is a current collector, the material is a titanium plate with the thickness of 2mm, the titanium plate is coated and pressed with a layer of lithium ion storage active material as a lithium storage layer (each surface of the current collector plate is coated with 23mm, the total thickness of two sides is 46 mm), and the outermost part is coated with a layer of lithium ion selective permeation material (each surface is coated with 100um, the total thickness of two sides is 200 um).
The storage material of the inner layer lithium ions is artificial graphite, and the national standard type AG-CMB-I-24-355. The technical requirements are as follows: the particle D50 is 24.5+ -2 um, D max Less than or equal to 60um, the fixed carbon content is more than or equal to 99.97%, the graphitization degree is more than or equal to 94%, and the powder compaction density is more than or equal to 1.6g/cm 3 The first charge specific capacity is more than or equal to 355mAh/g, and the first coulomb efficiency is more than or equal to 95%. The cyclic utilization performance is more than 6000 times.
The selective permeation material of the outer layer lithium ions is lithium ion positive electrode material nano LiFePO 4 . Materials are selected according to the requirements of national standard GB/T33822-2017: li content 4.3+ -0.3% and Fe content 34.0+/-2.0%, P content 19.5+/-1.5%, average particle diameter of electron microscope less than 100nm, secondary agglomerate particle less than 30um, tap density not less than 0.5g/cm 3 ，BET≤30m 2 And/g, wherein the volume resistivity of the product is less than or equal to 40. Delta. Cm. The specific capacity of the first discharge is more than or equal to 160mAh/g, the coulomb efficiency is more than or equal to 94%, the cycle performance requirement is that the cycle is 100 times, and the capacity is maintained to be more than 95%.
The manufacturing method of the electrode with the composite structure comprises the following steps:
(1) Firstly, respectively mixing artificial graphite, a binder and a solvent according to 30 percent: 20%:50% of mixed materials and size mixing; the binder is PVDF, and the solvent is NMP (N-methylpyrrolidone); coating the slurry on a titanium plate, rolling and forming, wherein the pressure is 1MPa, and drying at 120 ℃ to obtain a lithium storage layer pole piece; (preparation of slurry, lithium ion batteries, guo Bing, 2005.8, university of south and middle school Press, P257-258)
(2) Roughening the surface of the formed lithium storage layer pole piece, wherein the surface roughness Ra value is 100um;
(3) Respectively mixing nano lithium iron phosphate, a binder and a solvent according to 60 percent: 20%: mixing the materials uniformly in a proportion of 20%, and preparing slurry; the binder is PVDF, and the solvent is NMP; (the preparation method of the slurry is shown in lithium ion batteries, guo Bing and the like, 2005.8, university of middle and south China press, P257-258); uniformly coating the slurry on a lithium storage layer material, and drying at 105-120 ℃ for 12 hours; repeating the coating-drying operation after drying; coating and drying for 10 times, so that the surface of the manufactured electrode has no cracks and leakage points; thus obtaining the electrode with the composite structure.
Application of the electrode of the composite structure of the embodiment: the obtained electrode with the composite structure is taken as a positive electrode, an iron sheet is taken as a negative electrode, and the electrode is put into seawater. The iron sheet dissolves, releases electrons, the composite electrode obtains electrons, and absorbs lithium ions in seawater. And after the iron sheet is dissolved, the iron sheet is replaced to continue the reaction until the composite electrode is saturated by adsorbing lithium ions. Taking out the composite electrode with saturated adsorption as anode, fe 2+ The electrode is used as a cathode, and the electrode pair is electrified to release lithium ions into the extracting solution, so that the process of extracting lithium from seawater is realized.
The electrode with the composite structure can use the iron sheet as a negative electrode, and the lithium extraction process in the sea water is realized by utilizing the characteristic that the iron sheet is automatically dissolved in the sea water without electrifying. The electrode with the composite structure of the embodiment has the lithium adsorption capacity of 82mg/g, the single electrode lithium storage capacity of 2.2 kg (calculated according to metal lithium) and the cycle performance of 6000 times.
Example 2
The electrode of the composite structure of this embodiment is made up of three parts, the innermost is the current collector, the material is 4mm thick steel bar, the steel bar is coated and pressed the storage active material of a layer of lithium ion as the lithium storage layer (each surface is coated 15mm, the total thickness of both sides is 30 mm), the outermost is coated a layer of selective permeable material of lithium ion (each surface is coated 75um, the total thickness of both sides is 150 um).
The storage material of the inner layer lithium ion is hard carbon, the granularity D50 is 8.0-10.0 um, D max The fixed carbon is not less than 30 mu m, the powder compaction density is not less than 1.0g/cm < 3 >, and the first-time charging specific capacity is not less than 450mAh/g.
The selective permeation material of the outer layer lithium ions selects the lithium ion positive electrode material LiMn2O4. The materials were selected as required by YS/T677-2016: li content of 4.2+/-0.4%, mn content of 58.0+/-2.0%, D50 of 6.0-12.0, dmax less than or equal to 100um, tap density more than or equal to 1.1g/cm 3 ，BET≤0.4~1.2m 2 And/g, the specific capacity of the first discharge is more than or equal to 110mAh/g, the coulomb efficiency is more than or equal to 90%, the cycle performance is required to be cycled for 100 times, and the capacity is kept to be more than 85%.
The manufacturing method of the electrode with the composite structure comprises the following steps:
(1) Firstly, respectively mixing a lithium ion storage material, a binder and a solvent according to 40 percent: 10%:50% of the weight percentage, mixing and pulping. The binder is preferably PVDF, and the solvent is preferably NMP (N-methylpyrrolidone). Coating the slurry on a current collector, extruding and forming, wherein the pressure is 0.8-1.2 mpa, and drying at 110 ℃ to obtain a lithium storage layer pole;
(2) Roughening the surface of the formed lithium storage layer pole rod, wherein the surface roughness Ra value is 140um;
(3) Lithium ion selectively permeable material, binder and solvent are respectively mixed according to 80 percent: 15%: mixing evenly in proportion of 5%, and preparing into slurry; the binder is PVDF, and the solvent is NMP; uniformly coating the slurry on a lithium storage layer material, and drying at 105-120 ℃ for 12 hours; repeating the coating-drying operation after drying; coating and drying for 15 times, so that the surface of the manufactured composite electrode has no cracks and leakage points; thus obtaining the electrode with the composite structure.
Application of the electrode of the composite structure of the embodiment: and (3) taking the processed composite structure electrode as a cathode, taking an iron rod as an anode, putting the anode into sea water, introducing 0.8-1.2V voltage, extracting lithium at constant voltage, and stopping operation when the current is reduced to below 0.05 mA. And (3) taking the composite electrode with saturated adsorption as an anode and the new composite electrode as a cathode, and electrifying a formed electrode pair to release lithium ions into the extracting solution, so that the process of extracting lithium from seawater is realized.
The electrode with the composite structure of the embodiment has the adsorption capacity of lithium reaching 105mg/g, the single electrode lithium storage capacity reaching 1.7 kg (calculated according to metal lithium), and the cycle performance reaching 5000 times.
Example 3
The electrode of the composite structure of this embodiment is composed of three parts, the innermost part is a current collector, the material is a copper bar with the thickness of 4mm, the copper bar is externally coated with a layer of lithium ion storage active material pressed as a lithium storage layer (each surface is coated with 10mm, the total thickness of two sides is 20 mm), and the outermost part is coated with a layer of lithium ion selective permeation material (each surface is coated with 30um, the total thickness of two sides is 60 um).
The storage material of the inner layer lithium ion is a silicon-carbon negative electrode, the granularity requirement D50 is 8.0-10.0 um, and D max The fixed carbon is not less than 30 mu m, the powder compaction density is not less than 1.0g/cm < 3 >, and the first-time charging specific capacity is not less than 450mAh/g.
The selective permeation material of the outer layer lithium ions is Li in lithium ion conductor material lithium lanthanum titanium oxide 3x La (2/3)-x TiO 3 (0<x<0.16 With a specific component ratio of Li 0.33 La 0.56 TiO 3 。Li 0.33 La 0.56 TiO 3 Is a commercial product prepared by a solid phase method.
The manufacturing method of the electrode with the composite structure comprises the following steps:
(1) Firstly, respectively mixing a lithium ion storage material, a binder and a solvent according to 35 percent: 15%:50% of the weight percentage, mixing and pulping. The binder is PVDF, and the solvent is NMP (N-methylpyrrolidone); coating the slurry on a current collector, extruding and forming, wherein the pressure is 1.2Mpa, and drying at 110 ℃ to obtain a lithium storage layer pole;
(2) Roughening the surface of the formed lithium storage layer pole, wherein the surface roughness Ra value is 140-180 mu m;
(3) The lithium ion selective permeation material, the binder and the solvent are respectively prepared according to 28 percent: 22%: mixing at a ratio of 50% uniformly, and concocting into slurry. The binder is PVDF, and the solvent is NMP; uniformly coating the slurry on a lithium storage layer material, and drying at 105-120 ℃ for 12 hours; repeating the coating-drying operation after drying; coating and drying for 20 times, so that the surface of the manufactured composite electrode has no cracks and leakage points; thus obtaining the electrode with the composite structure.
Application of the electrode of the composite structure of the embodiment: and (3) taking the processed composite structure electrode as a cathode, taking an iron rod as an anode, putting the anode into sea water, introducing 0.9-1.6V voltage, extracting lithium at constant voltage, and stopping operation when the current is reduced to below 0.05 mA. And taking out the composite electrode with saturated adsorption as an anode, and electrifying the composite electrode with lithium ion desorption or the new composite electrode as a cathode to form an electrode to release lithium ions into the extracting solution, thereby realizing the process of extracting lithium from seawater.
The electrode with the composite structure of the embodiment has the lithium adsorption capacity of 140mg/g, the single electrode lithium storage capacity of 1.4 kg (calculated according to metal lithium) and the cycle performance of 6000 times.
Example 4
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 2, except that: the lithium storage layer is made of silicon oxide material (SiO) with the thickness of 10mm (each surface is coated with 5mm, the total thickness of two sides is 10 mm), and the selective permeation layer is LiCl 2Al (OH) with the thickness of 80um (each surface is coated with 40um, the total thickness of two sides is 80 um) 3 ·nH 2 O。
The electrode with the composite structure of the embodiment has the lithium adsorption capacity reaching 125mg/g, the single electrode lithium storage capacity reaching 1.9 kg (calculated according to metal lithium), and the cycle performance reaching 3000 times.
Example 5
The electrode with the composite structure of the embodiment, the manufacturing method and the application are basically the same as those of the embodiment 3, and the difference is that: the selectively permeable layer was 40um thick (20 um applied per side, 40um total thickness on both sides) of Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 （LATP）、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) molar ratio 1:1 mixture.
The electrode with the composite structure of the embodiment has the adsorption capacity of 138mg/g of lithium, the single electrode has the lithium storage capacity of 1.4 kg (calculated by metal lithium), and the cycle performance is up to 6000 times. In the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 10:1, molar ratio lithium ion/sodium ion is 5:1.
example 6
The electrode with the composite structure of the embodiment, the manufacturing method and the application are basically the same as those of the embodiment 3, and the difference is that: the selectively permeable layer was 30um thick (15 um applied per side, 30um total thickness on both sides) of Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 （LAGP）。
The electrode with the composite structure of the embodiment has the lithium adsorption capacity reaching 133mg/g, the single electrode lithium storage capacity reaching 1.4 kg (calculated according to metal lithium), and the cycle performance reaching 6000 times. In the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 8:1, molar ratio lithium ion/sodium ion is 7:1.
example 7
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 3, except that: the selectively permeable layer was 40um thick (20 um applied on each side, 40um total thickness on both sides) of lithium lanthanum zirconium oxide (Li 7 La 3 Zr 2 O 12 ，LLZO）。
The composite structure electrode of the embodiment has the lithium adsorption capacity of 142mg/g, the single electrode lithium storage capacity of 1.4 kg (calculated according to metal lithium) and the cycle performance of 6000 times. In the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 20:1, molar ratio lithium ion/sodium ion is 1:1.
example 8
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 1, except that: the lithium storage layer adopts graphite with the thickness of 5mm (each surface is coated with 2.5mm, the total thickness of two sides is 5 mm), and the selective permeation layer is 200um thick (each surface is coated with 100um, the total thickness of two sides is 200 um) 4 Ti 5 O 12 。
The electrode with the composite structure can use the iron sheet as a negative electrode, and the lithium extraction process in the sea water is realized by utilizing the characteristic that the iron sheet is automatically dissolved in the sea water without electrifying. The electrode with the composite structure of the embodiment has the lithium adsorption capacity of 82mg/g, the single electrode lithium storage capacity of 0.2 kg (calculated according to metal lithium) and the cycle performance of 6000 times.
Example 9
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 1, except that: the lithium storage layer adopts graphite with the thickness of 1mm (each surface is coated with 0.5mm, the total thickness of two sides is 1 mm), and the selective permeation layer is 100um thick (each surface is coated with 50um, the total thickness of two sides is 100 um) 7 Ti 5 O 12 。
The electrode with the composite structure can use the iron sheet as a negative electrode, and the lithium extraction process in the sea water is realized by utilizing the characteristic that the iron sheet is automatically dissolved in the sea water without electrifying. The electrode with the composite structure of the embodiment has the lithium adsorption capacity of 82mg/g, the single electrode lithium storage capacity of 0.05 kg (calculated according to metal lithium) and the cycle performance of 6000 times.
Example 10
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 1, except that: the lithium storage layer adopts graphite with the thickness of 0.2mm (each surface is coated with 0.1mm, the total thickness of two sides is 0.2 mm), and the selective permeation layer is 80um thick (each surface is coated with 40um, the total thickness of two sides is 80 um) 2 Ti 3 O 7 。
The electrode with the composite structure can use the iron sheet as a negative electrode, and the lithium extraction process in the sea water is realized by utilizing the characteristic that the iron sheet is automatically dissolved in the sea water without electrifying. The electrode with the composite structure of the embodiment has the lithium adsorption capacity reaching 85mg/g, the single electrode lithium storage capacity reaching 0.009 kg (calculated according to metal lithium), and the cycle performance reaching 6000 times.
Example 11
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 1, except that: the selectively permeable layer is Li 1-x FePO 4 （0<x≤1)。
The electrode of the composite structure of this example has substantially the same extraction effect as that of example 1, but the selectively permeable layer material contains less lithium and the cost is 30% lower than that of example 1.
Example 12
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 1, except that: the selectively permeable layer is Li 1-x Mn 2 O 4 （0<x≤1)。
The electrode of the composite structure of this example has substantially the same extraction effect as that of example 1, but the selectively permeable layer material contains less lithium and the cost is 40% lower than that of example 1.
Example 13
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 1, except that: the selectively permeable layer is Li 7-x Ti 5 O 12 （0<x≤4）。
The electrode of the composite structure of this example has substantially the same extraction effect as that of example 1, but the selectively permeable layer material contains less lithium and the cost is 20% lower than that of example 1.
Example 14
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 3, except that: the selectively permeable layer is composed of two layers, the inner layer is 150um thick (75 um coated on each surface, 150um total thickness on both sides) LiFePO 4 The outer layer is of lithium lanthanum titanium oxide Li with thickness of 40um (each surface is coated with 20um, total thickness of two sides is 40 um) 0.33 La 0.56 TiO 3 。
The electrode with the composite structure of the embodiment has the same lithium ion extraction effect as that of embodiment 3; in the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 40:1, molar ratio lithium ion/sodium ion is 20:1. in the embodiment, two layers of different selective permeation layer materials are adopted, so that the isolation effect on impurity sodium and magnesium is better.
Example 15
The electrode of the composite structure of this embodiment, and the manufacturing method and application are basically the same as those of embodiment 3, except that: the selectively permeable layer is composed of two layers, and the inner layer is 80um thick (40 um coated on each surface and 80um total thickness on both sides) LiFePO 4 The outer layer was 20um thick (10 um applied on each side, 20um total thickness on both sides) LiCl 2Al (OH) 3 ·nH 2 O，。
The electrode with the composite structure of the embodiment has the same lithium ion extraction effect as that of embodiment 3; in the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 30:1, molar ratio lithium ion/sodium ion is 20:1. in the embodiment, two layers of different selective permeation layer materials are adopted, so that the isolation effect on impurity sodium and magnesium is better; liCl 2Al (OH) 3 ·nH 2 The O coating also has good hydrophilicity, and is favorable for adsorbing lithium ions on the surface.
Claims (14)
1. The electrode with the composite structure is characterized by comprising a lithium storage layer and a selectively permeable layer coated on the surface of the lithium storage layer;
the lithium storage layer is made of one or more of carbon material, silicon-carbon material and silicon-oxygen material;
the selectively permeable layer is made of lithium ion positive electrode material, lithium titanate material, lithium lanthanum titanium oxide, LATP material, LAGP material, liCl 2Al (OH) 3 ·nH 2 O material, garnet-structured Li 5+x La 3 M 2 O 12 One or more than two materials; the Li is 5+x La 3 M 2 O 12 M in (2) represents one or more of Nb, ta and Zr;
the electrode of the composite structure further comprises a current collector; the lithium storage layer is covered on the surface of the current collector and is positioned between the current collector and the selective permeation layer; the thickness of the current collector is 1-5 mm; the thickness of one side of the lithium storage layer is 0.1-50 mm; the thickness of one side of the selectively permeable layer is 5-200 um.
2. The composite structure electrode of claim 1, wherein the carbon material is one or more of graphite, hard carbon, soft carbon, and graphene.
3. The electrode of claim 1, wherein the lithium storage layer is made of a material having a fixed carbon content of 99.9% or more, a D50 particle size of 5.0 to 30.0 μm, and D max Graphite with graphitization degree not less than 90% and not more than 70 μm;
or the fixed carbon content is more than or equal to 99%, the granularity of D50 is 5.0-10.0 um, and D max Not more than 30um, and the compacted density of the powder not less than 1.0g/cm 3 A hard carbon negative electrode of (a);
or the SiO content is more than or equal to 20%, the C content is less than or equal to 80%, the D50 is 10-20 um, and the D max Not more than 40um, compaction density not less than 1.0g/cm 3 Silicon oxide material SiO;
or Si content is more than or equal to 2%, carbon content is less than or equal to 98%, D50 is 10-20 um, D max Not more than 32um, compaction density not less than 1.0g/cm 3 Silicon carbon material SiC of (a).
4. The composite structure electrode of claim 1 wherein the selectively permeable layer material is LiFePO 4 、LiMn 2 O 4 、LiCoO 2 、LiNi 1-a-b Co a Mn b O 2 、Li 4 Ti 5 O 12 、Li 7 Ti 5 O 12 、Li 1-c FePO 4 、Li 1-d Mn 2 O 4 、Li 1- e CoO 2 、Li 1-f Ni 1-g-h Co g Mn h O 2 、Li 7-i Ti 5 O 12 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 、Li 7 La 3 Zr 2 O 12 、Li 3j La (2/3)-j TiO 3 、LiCl·2Al(OH) 3 ·nH 2 One or more than two of O, wherein 0<a≤1，0<b≤1，0<c≤1，0<d≤1，0<e≤1，0<f≤1，0<g≤1，0<h≤1，0<i≤4，0<j<0.16。
5. The electrode of claim 4, wherein the selectively permeable layer is made of LiFePO with Li content of 4.3+ -0.3%, fe content of 34.0+ -2.0%, P content of 19.5+ -1.5%, electron microscope average particle size of less than 100nm, and secondary agglomerate particle size of less than 30um 4 ；
Or Mn 58+ -2.0%, li 4.2+ -0.4%, D50 of 6-14 um, D max LiMn less than or equal to 100um 2 O 4 ；
Or Li content 7.0+ -0.5%, D50 of 4-25 um, D max LiCoO less than or equal to 70um 2 ；
Or Li content 7.0+ -0.5%, D50 of 4-25 um, D max LiNi less than or equal to 70um 1-a-b Co a Mn b O 2 Wherein 0 is<a≤1，0<b≤1；
Or the Ti content is more than or equal to 45%, the Li content is 6.0+/-1.0%, and the D50 is 0.5-10 um of Li 4 Ti 5 O 12 。
6. The composite structure electrode of claim 1 or 4, wherein the selectively permeable layer has a bilayer or multilayer structure.
7. The composite structure electrode of claim 6 wherein the selectively permeable layer is an inner layer LiFePO 4 Double-layer structure of outer layer lithium lanthanum titanium oxide, or inner layer LiFePO 4 Outer LiCl 2Al (OH) 3 ·nH 2 O double layer structure.
8. The method for manufacturing an electrode of a composite structure according to any one of claims 1 to 7, comprising the steps of:
(1) Mixing the lithium ion storage material and the binder uniformly to form slurry, coating the slurry on a current collector, rolling or extrusion molding, and drying to obtain a pole piece or pole rod containing a lithium storage layer;
(2) Carrying out surface roughening treatment on the pole piece or pole rod containing the lithium storage layer;
(3) Mixing the lithium ion selective permeation material and the binder uniformly to obtain slurry, coating the slurry on a pole piece or pole rod of the lithium storage layer with the surface roughened, and drying to obtain the electrode with the composite structure;
in the step (3), the coating times are one or more than two times; when the coating is performed twice or more, the next coating is performed after the previous coating is completely dried.
9. The method for manufacturing the electrode with the composite structure according to claim 8, wherein the drying temperature is 80-600 ℃; in the step (1), the pressure of rolling or extrusion molding is 0.1-5 MPa; in the step (2), surface roughening treatment is carried out to ensure that the surface roughness Ra value is 20-200 um; in the step (3), the coating times are 3-30 times.
10. The use of the electrode of the composite structure according to any one of claims 1 to 7 or the electrode of the composite structure obtained by the method for manufacturing the electrode of the composite structure according to any one of claims 8 to 9, wherein the electrode of the composite structure is used as a positive electrode and the metal is used as a negative electrode to form an electrochemical device; introducing lithium-containing liquid, extracting lithium by self-discharge through metal dissolution, and gradually adsorbing lithium ions on the electrode of the composite structure;
or the electrode of the composite structure is taken as a cathode, and the metal is taken as an anode to form an electrochemical device; and introducing lithium-containing liquid, extracting lithium at constant pressure, and gradually adsorbing lithium ions on the electrode of the composite structure.
11. The use of the composite structured electrode according to claim 10, wherein the method for releasing lithium ions in the lithium ion-adsorbed composite structured electrode into the extraction solution is:
method A:
fe with the electrode of the composite structure absorbing lithium ions as an anode 2+ The electrode is a cathode to form an electrochemical device, the electrolyte is used as extracting solution, and lithium ions are released into the electrolyte by electrifying;
or method B:
the electrode of the composite structure is used as a cathode, the electrode of the composite structure absorbing lithium ions is used as an anode, an anion exchange membrane is used for separating two chambers to form an electrochemical device, lithium-containing liquid is introduced into the cathode chamber, electrolyte serving as extracting solution is arranged in the anode chamber, lithium is extracted at constant pressure, and lithium ions enter the electrolyte.
12. The use of an electrode of a composite structure according to claim 11, wherein the electrolyte is a sodium chloride solution, the molar concentration of chloride ions in the electrolyte being the same as the total molar concentration of anions of the lithium-containing liquid.
13. The use of the electrode of the composite structure according to claim 12, wherein the chloride ion content in the electrolyte is 10-100 g/l.
14. The use of an electrode of a composite structure according to any one of claims 10 to 13, wherein the constant voltage lithium extraction voltage is 0 to 2v; and stopping constant-voltage lithium extraction when the adsorption saturation of the electrode or the current is reduced to below 0.05 mA.
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