CN115679122A - Electrode with composite structure and manufacturing method and application thereof - Google Patents
Electrode with composite structure and manufacturing method and application thereof Download PDFInfo
- Publication number
- CN115679122A CN115679122A CN202211474457.7A CN202211474457A CN115679122A CN 115679122 A CN115679122 A CN 115679122A CN 202211474457 A CN202211474457 A CN 202211474457A CN 115679122 A CN115679122 A CN 115679122A
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrode
- composite structure
- equal
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 112
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 148
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 95
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000003860 storage Methods 0.000 claims abstract description 68
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims description 81
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 27
- 238000000605 extraction Methods 0.000 claims description 25
- 239000010936 titanium Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 23
- 229910052742 iron Inorganic materials 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 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
- 230000005540 biological transmission Effects 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 10
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 10
- 238000007788 roughening Methods 0.000 claims description 9
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 229910013716 LiNi Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010405 anode material 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
- 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
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 5
- 229910010710 LiFePO 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
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002245 particle Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- 229910018871 CoO 2 Inorganic materials 0.000 claims description 3
- 238000005087 graphitization Methods 0.000 claims description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910012820 LiCoO Inorganic materials 0.000 claims description 2
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005349 anion exchange Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 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
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 21
- 239000013535 sea water Substances 0.000 description 19
- 239000011572 manganese Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 229920006395 saturated elastomer Polymers 0.000 description 9
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 239000011149 active material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 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
- 239000002994 raw material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000005056 compaction Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 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
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 239000010959 steel Substances 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 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
- 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
- 239000003463 adsorbent Substances 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
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000013078 crystal Substances 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
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 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
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000047 product Substances 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
- 229910020717 Li0.33La0.56TiO3 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
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 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
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 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
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000674 effect on sodium Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 238000009413 insulation Methods 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
- 150000002641 lithium Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052708 sodium 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
- 230000005477 standard model Effects 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 comprises a lithium storage layer and a selective permeation 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 lithium adsorption capacity, high lithium ion storage capacity and high cycling 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 the surface coating can be repaired by adding the coating after being damaged.
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, and the difficulty of extracting lithium is high. The traditional method mainly applies 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 a new lithium extraction technology is imperative, and electrochemical lithium extraction has certain selectivity and becomes a research hotspot at present.
Kanoh et al, 1993, proposed the use of lambda-MnO 2 as a working electrode for electrochemical lithium extractionUsed for electrochemical extraction of lithium. Lithium ion in LiMn 2 O 4 The reaction equation of the extraction and lithium insertion in the electrode material and the lithium insertion are shown in formula (1) to formula (3):
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) positive electrode: 2 lambda-MnO 2 + Li + + e − =LiMn 2 O 4 (3)
The method adopts LiMn 2 O 4 The problem of the dissolution loss of manganese and poor conductivity of the electrode follow-up occurs, and in addition, the electrode material can be corroded in seawater or brine.
In the research on the lithium intercalation behavior of lithium iron phosphate in a lithium ion aqueous solution, dan Xiaoqian firstly proposes a concept of extracting lithium from an aqueous solution by using a lithium iron phosphate electrode. CN102049238A is an ionic sieve for selectively extracting lithium and application thereof, and discloses a method for preparing a lithium iron phosphate ionic sieve and application thereof. CN110777390A discloses an electrochemical method for self-driven lithium extraction based on a rocking chair type structure electrode system, which assembles lithium-poor state and lithium-rich state positive electrode materials into a working electrode to perform electrochemical lithium extraction.
In the above-disclosed methods, the lithium ion battery positive electrode material is used as an active material for lithium adsorption and storage. However, the anode materials of lithium ion batteries, such as lithium iron phosphate, ternary lithium manganese oxide and lithium manganese oxide, which are widely used at present, have the problem of low electronic conductivity and ionic conductivity. So that only thin electrodes can be used when manufacturing electrodes. In addition, the anode material of the lithium ion battery generally contains low lithium, such as lithium iron phosphate saturated state, and contains lithium up to 4.4%.
The factors determine that the adsorption capacity of the lithium ion battery anode material used as an electrochemical lithium extraction system is low, the best lithium iron phosphate lithium extraction system is made on the market, and the adsorption capacity of lithium is only 30mg/g. In actual operation, the adsorption is saturated very quickly. Frequent intercalation and deintercalation operations lead to dissolution loss and exfoliation of the lithium extraction active material. The electrode has high maintenance cost and low lithium extraction efficiency.
In summary, the general problems of electrochemical lithium extraction are as follows:
(1) The electron conductivity is low. LiCoO 2 、LiMn 2 O 4 And LiFePO 4 Are poor electron conductors, each having a conductivity of 10 -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. The reported lithium extraction working electrode LiMn 2 O 4 And LiFePO 4 Etc., the theoretical storage amounts were 38.6mg/g and 44.3mg/g, respectively. The theoretical storage lithium capacity is very low.
(3) The cycling stability is poor. Li 1-x After multiple cycles, the disproportionation reaction of trivalent manganese ions is easy to occur to Mn2O4/LiMn2O4, which causes the dissolution loss of manganese and the reduction of cycle performance. Li 1-x Capacity also decays during the FePO4/LiFePO4 recycle process.
(4) The equipment cost is high. The existing lithium extraction electrode has low electronic conductivity and low lithium ion storage capacity. More equipment is needed and the investment cost is high under the same lithium salt yield.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art and provide an electrode with a composite structure, high lithium adsorption capacity and good cycling stability, and a manufacturing method and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: an electrode with a composite structure comprises a lithium storage layer and a selective permeation layer coated on the surface of the lithium storage layer;
the material of the lithium storage layer is one or more than two of a carbon material, a silicon-carbon material and a silicon-oxygen material;
the material of the selective permeation layer is lithium ion anode 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 of the materials; the Li 5+x La 3 M 2 O 12 M in (A) 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 covers the surface of the current collector and is positioned between the current collector and the selective permeation layer.
Preferably, the thickness of the current collector is 1 to 5mm; the current collector can be in the conventional shapes of a sheet shape, a rod shape and the like, and a through hole can be formed in the current collector; the current collector can be a commercial product directly, and metal materials such as titanium, steel, copper and aluminum can also be used as the current collector.
Preferably, the thickness of the single surface of the lithium storage layer is 0.1 to 50mm, and more preferably 5 to 25mm.
Preferably, the thickness of the single surface of the selective permeation layer is 5 to 200um, and more preferably 10 to 100um.
Preferably, the carbon material is one or more of graphite, hard carbon, soft carbon, and graphene.
Preferably, the material of the lithium storage layer has a fixed carbon content of more than or equal to 99.9 percent; d50 granularity is 5.0-30.0 um max Less than or equal to 70um; graphite with the graphitization degree of more than or equal to 90 percent; the lithium storage capacity of the material is more than or equal to 80mg/g, and the recycling frequency of the material as an electrode can reach 4000 times.
Preferably, the material of the lithium storage layer has a fixed carbon content of more than or equal to 99 percent; d50 granularity is 5.0-10.0 um max Less than or equal to 30um; the compacted density of the powder is more than or equal to 1.0g/cm 3 The hard carbon negative electrode of (1); the lithium storage capacity of the material is more than or equal to 100mg/g, and the recycling frequency of the material as an electrode is more than 5000 times.
Preferably, the material of the lithium storage layer has the SiO content of more than or equal to 20 percent and the C content of less than or equal to 80 percent; d50 is 10 to 20um max Less than or equal to 40um; the compacted density is more than or equal to 1.0g/cm 3 SiO, a silicon oxide material; the lithium storage capacity of the material is more than or equal to 120mg/g, and the recycling frequency of the material as an electrode is more than 1000 times.
Preferably, the material of the lithium storage layer has Si content more than or equal to 2 percent and carbon content less than or equal to 98 percent; d50 is 10 to 20um max Less than or equal to 32um; the compaction density is more than or equal to 1.0g/cm 3 The silicon carbon material SiC; the lithium storage capacity of the material is more than or equal to 130mg/g, and the recycling frequency of the material as an electrode is more than 2000 times.
Preferably, the material of the selective permeation 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 selective transmission 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 size of less than 100nm and secondary agglomerate particle size of less than 30um 4 。
Preferably, the material of the selective permeation layer has a Mn content of 58 +/-2.0% and a Li content of 4.2 +/-0.4%; d50 is 6-14um max LiMn less than or equal to 100um 2 O 4 。
Preferably, the selective permeation layer is made of a material with the Li content of 7.0 +/-0.5 percent and the D50 of 4 to 25um max LiCoO less than or equal to 70um 2 。
Preferably, the material of the selective permeation layer has a Li content of 7.0 +/-0.5 percent and a D50 of 4-25um 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 material of the selective transmission layer contains more than or equal to 45% of Ti, 6.0 +/-1.0% of Li and 0.5-10um of D50 4 Ti 5 O 12 。
Preferably, the material of the selective permeation 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 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 The lithium-deficient compound 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 selective permeation 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 Being a LATP material, li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 Is a LAGP material; can be purchased directly or in 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 a high-temperature solid phase method.
Preferably, the material of the selective permeation layer is Li 7 La 3 Zr 2 O 12 . The material is a lithium lanthanum zirconium oxide with a garnet structure, 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 selective permeation 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 as TiO 2 ，Li 2 CO 3 ，La 2 O 3 Is obtained by high-temperature roasting of raw materials.
Preferably, the material of the selective transmission layer is LiCl 2Al (OH) 3 ·nH 2 And O. The material can be purchased directly or through LiCl or AlCl 3 Reacting with alkali.
Preferably, the material of the selective permeation layer is the above-mentioned 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, 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。
Preferably, the permselective layer has a double or multi-layer structure.
More preferably, the selective permeation layer is an inner layer LiFePO 4 The outer layer is of a double-layer structure of lithium lanthanum titanium oxide.
More preferably, the selective permeation layer is an inner layer LiFePO 4 Outer layer LiCl 2Al (OH) 3 ·nH 2 A double-layer structure of O.
The manufacturing method of the electrode with the composite structure comprises the following steps:
(1) Uniformly mixing a lithium ion storage material and a binder to form slurry, coating the slurry on a current collector, rolling or extruding and molding, and drying to obtain a pole piece or a pole rod containing a lithium storage layer; (see "lithium ion batteries", guo Bing et al, 2005.8, zhongnan university Press, P257 to 258.)
(2) Carrying out surface roughening treatment on the pole piece or the pole rod containing the lithium storage layer;
(3) Uniformly mixing a lithium ion selective transmission material and a binder to form slurry, coating the slurry on a pole piece or a pole rod which is subjected to surface roughening treatment and contains a lithium storage layer, and drying to obtain an electrode with a composite structure; (the method for producing the slurry can be referred to lithium ion batteries Guo Bing, 2005.8, zhongnan university Press, P257 to 258.)
In the step (3), the coating times are one or more than two; when the coating is performed twice or more, the next coating is performed after the previous coating is completely dried.
Preferably, the temperature of drying is 80 to 600 ℃.
Preferably, in the step (1), the pressure for rolling or extrusion molding is 0.1 to 5MPa.
Preferably, in the step (2), the surface roughening treatment is performed so that the surface roughness Ra is 20 to 200um.
Preferably, in the step (3), the coating times are 3 to 30; the multiple coating can make the surface of the manufactured composite electrode have no cracks or leak points.
The composite structure electrode is used as a positive electrode, and metal is used as a negative electrode to form an electrochemical device; introducing a lithium-containing solution, and extracting lithium by metal dissolution and self-discharge; obtaining electrons from the composite electrode of the anode; 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 is a metal capable of dissolving self-discharge in the lithium-containing liquid under the condition, such as: iron, aluminum, zinc and manganese.
Or the electrode with the composite structure is taken as a cathode, and metal is taken as an anode to form an electrochemical device; and introducing a lithium-containing solution, extracting lithium at constant pressure, and gradually adsorbing lithium ions on the electrode with the composite structure. Common lithium-containing liquids include seawater, salt lake water, and the like.
Preferably, the voltage for constant-voltage lithium extraction is 0 to 2V.
Preferably, the constant-voltage lithium extraction is stopped when the electrode adsorption saturation or current drops below 0.05 mA.
The reaction that occurs when the composite electrode is adsorbed in the lithium-containing solution 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 C, obtaining electrons, and transferring lithium ions 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 composite-structure electrode, the method for releasing lithium ions in the composite-structure electrode adsorbed with lithium ions into the extracting solution is as follows:
the method A comprises the following steps: using an electrode of a composite structure adsorbing lithium ions as an anode, fe 2+ The iron 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, taking out the composite electrode, and Fe 2+ The iron electrode is formed into a battery, and the reaction generated by electrifying 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 extracting solution.
Preferably, in the application of the composite-structure electrode, the method for releasing lithium ions in the composite-structure electrode adsorbed with lithium ions into the extracting solution is as follows:
the method B comprises the following steps: the electrode with the composite structure is used as a cathode, the electrode with the composite structure absorbing lithium ions is used as an anode, an anion exchange diaphragm 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 the 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 to 100g/l.
Preferably, the voltage of the constant-voltage lithium extraction is 0 to 2V.
Preferably, the 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 the us Versogen brand membrane, or a domestic anion membrane, such as the GCAM series anion membrane products of the state of the art. Monovalent anion exchange membranes are also an option, but at higher cost.
The reaction of the composite electrode in method B is as follows:
the reaction formula of the adsorption saturated composite electrode for releasing lithium ions is as follows:
Li x C = C + xLi + + xe-
the new composite electrode absorbs lithium ions according to the reaction formula:
C + xLi + + xe - = Li x C
the lithium ions in the lithium-containing solution are transferred to the electrode with the new composite structure, and the lithium ions in the electrode with the composite structure absorbed with the lithium ions are transferred to the extracting solution.
The composite electrode of the invention is composed of a plurality of layers, and the inner layer is mainly made of active materials for storing lithium ions, such as a carbon negative electrode and a silicon-carbon negative electrode. The material features high capacity of storing lithium ion, high electronic conductivity, high circulation times and low cost, and may be used in making thick electrode, even 50mm thick. The total amount of the lithium ions stored in the lithium storage layer is greatly increased; the selective permeation layer adopted by the outer layer can selectively permeate Li + Isolate most of Na + 、K + 、Mg 2+ When cations and anions are used, certain electronic insulation is required, self-discharge and electric leakage are reduced, and energy consumption is reduced; as a result of research, the inventors found that the following materials are suitable for making the selectively permeable layer, such as: the commonly used lithium ion battery anode material can selectively permeate lithium ions and has the characteristic of low electronic conductivity; one of the components of the solid electrolyte, inorganic lithium ion conductor such as LLTO and LLZO oxide, has vacancy on the structure surface to selectively allow lithium ion to pass through, and has lithium ion conductivity of 10 -3 ~10 -6 S/cm, as a component of the electrolyte, the electronic conductivity of LLTO and LLZO is extremely low; the other material is aluminum salt adsorbent, manganese ion sieve, titanium ion sieve, iron phosphate lithium ion sieve and cobalt acid lithium ion sieve, and can selectively adsorb lithium ions and be used for coating of composite electrode.
The invention has the beneficial effects that:
(1) The electrode with the composite structure has high lithium adsorption capacity, high lithium ion storage capacity and high cycling stability, and the equipment cost for manufacturing and applying the electrode with the composite structure is low; the electronic 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 and above, 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 the surface coating can be repaired by adding the coating after being damaged.
Detailed Description
The present invention is further illustrated by the following examples.
The starting materials used in the examples of the present invention were all obtained from conventional commercial sources.
Example 1
The electrode of the composite structure of the embodiment is composed of three parts, wherein the innermost part is a current collector, the material is a titanium plate with the thickness of 2mm, the titanium plate is coated with a storage active material for pressing a layer of lithium ions 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 selective permeation material for lithium ions (each surface is coated with 100um, and the total thickness of two sides is 200 um).
The storage material of the inner lithium ion is artificial graphite with the national standard model AG-CMB-I-24-355. The technical requirements are as follows: the D50 of the particles is 24.5 +/-2um max Less than or equal to 60um, the fixed carbon content is more than or equal to 99.97 percent, the graphitization degree is more than or equal to 94 percent, and the powder compaction density is more than or equal to 1.6g/cm 3 The first charging specific capacity is more than or equal to 355mAh/g, and the first coulombic efficiency is more than or equal to 95 percent. The recycling performance is more than 6000 times.
The selective permeation material of the outer layer lithium ions is lithium ion anode material nano LiFePO 4 . Selecting materials according to the requirements of national standard GB/T33822-2017: li content of 4.3 +/-0.3%, fe content of 34.0 +/-2.0%, P content of 19.5 +/-1.5%, average electron microscope grain size of less than 100nm, secondary agglomerate grain size of less than 30um, and tap density of 0.5g/cm or more 3 ，BET≤30m 2 And/g, the volume resistivity of the product is less than or equal to 40 Ω & cm. Specific capacity of first discharge is not less than160mAh/g, coulombic efficiency more than or equal to 94%, circulation performance requirement is 100 times, and capacity is kept more than 95%.
The method for manufacturing the electrode with the composite structure comprises the following steps:
(1) Firstly, respectively mixing artificial graphite, a binder and a solvent by 30%:20%:50 percent of the weight percentage, mixing the materials and mixing the slurry; PVDF is selected as a binder, and NMP (N-methyl pyrrolidone) is selected as a solvent; coating the slurry on a titanium plate, rolling and forming under the pressure of 1MPa, and drying at 120 ℃ to obtain a lithium storage layer pole piece; (the method for producing the slurry is described in lithium ion batteries Guo Bing, 2005.8, university Press of Zhongnan, P257 to 258.)
(2) Roughening the surface of the formed lithium storage layer pole piece, wherein the surface roughness Ra is 100 mu m;
(3) Respectively mixing the nano lithium iron phosphate, the binder and the solvent by 60%:20%: uniformly mixing 20% of the raw materials, and mixing to obtain slurry; PVDF is selected as a binder, and NMP is selected as a solvent; (the slurry preparation method is shown in lithium ion batteries, guo Bing and the like, 2005.8, university Press of China and south, 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 to make the surface of the manufactured electrode have no cracks and leak points; and obtaining the electrode with a composite structure.
Application of the electrode of the composite structure of the embodiment: and (4) putting the obtained electrode with the composite structure into seawater as a positive electrode and an iron sheet as a negative electrode. The iron sheet is dissolved to release electrons, and the composite electrode obtains the electrons and absorbs lithium ions in seawater. And after the iron sheet is dissolved, replacing the iron sheet and continuing to react until the composite electrode is saturated by absorbing lithium ions. Taking out the composite electrode with saturated adsorption to serve as an anode, and Fe 2+ The iron electrode is used as a cathode, and the formed 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, utilizes the characteristic that the iron sheet is automatically dissolved in seawater, does not need to be electrified, and realizes the process of extracting lithium in seawater. In the electrode with the composite structure, the lithium adsorption capacity reaches 82mg/g, the single-electrode lithium storage capacity reaches 2.2 kilograms (calculated according to metal lithium), and the cycle performance reaches 6000 times.
Example 2
The electrode with the composite structure comprises three parts, wherein the innermost part is a current collector and is made of a steel bar with the thickness of 4mm, the steel bar is coated with a storage active material for pressing a layer of lithium ions as a lithium storage layer (15 mm is coated on each surface, the total thickness of two sides is 30 mm), and the outermost part is coated with a layer of selective permeation material for lithium ions (75 um is coated on each surface, and the total thickness of two sides is 150 um).
Hard carbon is selected as the storage material of the lithium ion in the inner layer, the granularity requirement D50 is 8.0-10.0 um max Less than or equal to 30 mu m, more than or equal to 99 percent of fixed carbon, more than or equal to 1.0g/cm < 3 > of powder compaction density and more than or equal to 450mAh/g of first charge specific capacity.
The selective permeation material of the outer layer lithium ions is selected from a lithium ion positive electrode material LiMn2O4. Selecting materials according to requirements of YS/T677-2016: li content of 4.2 +/-0.4%, mn content of 58.0 +/-2.0%, D50 of 6.0-12.0, dmax of less than or equal to 100um, tap density of more than or equal to 1.1g/cm 3 ，BET≤0.4~1.2m 2 The specific discharge capacity for the first time is more than or equal to 110mAh/g, the coulombic efficiency is more than or equal to 90 percent, the cycle performance requirement is that the cycle is performed for 100 times, and the capacity is kept to be more than 85 percent.
The method for manufacturing 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 the proportion of 40%:10%:50 percent of the weight percentage, mixing the materials and mixing the slurry. The binder is preferably PVDF and the solvent is preferably NMP (N-methylpyrrolidone). Coating the slurry on a current collector, extruding and forming under the pressure of 0.8 to 1.2Mpa, and drying at 110 ℃ to obtain a lithium storage layer pole rod;
(2) Roughening the surface of the formed lithium storage layer pole rod, wherein the surface roughness Ra is 140 mu m;
(3) The lithium ion selective permeation material, the binder and the solvent are respectively mixed according to the proportion of 80%:15%:5 percent of the raw materials are uniformly mixed and prepared into slurry; PVDF is selected as a binder, and NMP is selected as a solvent; 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 to make the surface of the prepared composite electrode have no cracks and leak points; and obtaining the electrode with a composite structure.
Application of the electrode of the composite structure of the embodiment: and (3) putting the processed composite structure electrode serving as a cathode and an iron rod serving as an anode into seawater, introducing a voltage of 0.8-1.2V, extracting lithium at a constant voltage, and stopping operation when the current is reduced to be below 0.05 mA. And (3) taking the composite electrode with saturated adsorption as an anode and the new composite electrode as a cathode to form an electrode pair, and electrifying to release lithium ions into the extracting solution, thereby realizing the process of extracting lithium from seawater.
In the electrode with the composite structure of the embodiment, the lithium adsorption capacity reaches 105mg/g, the single-electrode lithium storage capacity reaches 1.7 kg (calculated according to metal lithium), and the cycle performance reaches 5000 times.
Example 3
The electrode of the composite structure of the embodiment is composed of three parts, wherein the innermost part is a current collector, the material is a copper bar with the thickness of 4mm, the copper bar is coated with a storage active material for pressing a layer of lithium ions 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 selective permeation material for lithium ions (each surface is coated with 30um, the total thickness of two sides is 60 um).
The storage material of the lithium ion in the inner layer is a silicon-carbon cathode, the granularity requirement D50 is 8.0-10.0 um max Less than or equal to 30 mu m, more than or equal to 99 percent of fixed carbon, more than or equal to 1.0g/cm < 3 > of powder compaction density and more than or equal to 450mAh/g of first charge specific capacity.
The selective transmission material of the lithium ions on the outer layer is Li in lithium lanthanum titanium oxide which is a lithium ion conductor material 3x La (2/3)-x TiO 3 (0<x<0.16 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 method for manufacturing the electrode with the composite structure comprises the following steps:
(1) Firstly, respectively mixing a lithium ion storage material, a binder and a solvent by 35%:15%:50 percent of the weight percentage, mixing the materials and mixing the slurry. PVDF is selected as a binder, and NMP (N-methyl pyrrolidone) is selected as a solvent; coating the slurry on a current collector, extruding and forming under the pressure of 1.2Mpa, and drying at 110 ℃ to obtain a lithium storage layer pole bar;
(2) Roughening the surface of the molded lithium storage layer pole rod, wherein the surface roughness Ra is 140-180um;
(3) The lithium ion selective permeation material, the binder and the solvent are respectively mixed according to the proportion of 28%:22%: mixing at a ratio of 50% uniformly, and making into slurry. PVDF is selected as a binder, and NMP is selected as a solvent; 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 to make the surface of the prepared composite electrode have no cracks and leak points; and obtaining the electrode with a composite structure.
Application of the electrode of the composite structure of the embodiment: and (3) putting the processed composite structure electrode serving as a cathode and an iron rod serving as an anode into seawater, introducing a voltage of 0.9-1.6V, extracting lithium at a constant voltage, and stopping operation when the current is reduced to be below 0.05 mA. And taking out the composite electrode which is saturated in adsorption, taking the composite electrode as an anode, taking the composite electrode for lithium ion desorption or a new composite electrode as a cathode, and electrifying the composite electrode to release lithium ions into the extracting solution, thereby realizing the process of extracting lithium from seawater.
In the electrode with the composite structure, the lithium adsorption capacity reaches 140mg/g, the single-electrode lithium storage capacity reaches 1.4 kg (calculated according to metal lithium), and the cycle performance reaches 6000 times.
Example 4
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 2, and the differences are as follows: the lithium storage layer is made of silicon oxide (SiO) material with 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 thickness of 80um (each surface is coated with 40um, the total thickness of two sides is 80 um) 3 ·nH 2 O。
In the electrode with the composite structure of the embodiment, the lithium adsorption capacity reaches 125mg/g, the single-electrode lithium storage capacity reaches 1.9 kg (calculated according to metal lithium), and the cycle performance reaches 3000 times.
Example 5
The electrode of the composite structure of the present embodiment, the manufacturing method and the application are basically the same as those of the embodiment.3, and the differences are as follows: the selectively permeable layer is 40um thick (20 um coated on each side, total thickness 40 on both sides)um) 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) 1:1 molar ratio mixture.
In the electrode with the composite structure, the lithium adsorption capacity reaches 138mg/g, the single-electrode lithium storage capacity reaches 1.4 kg (calculated according to metal lithium), and the cycle performance reaches 6000 times. In the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 10:1, the molar ratio of lithium ions/sodium ions is 5:1.
example 6
The electrode of the composite structure of the embodiment, the manufacturing method and the application are basically the same as those of the embodiment.3, and the differences are as follows: the selectively permeable layer is 30um thick (15 um coated on each side, 30um total thickness on both sides) Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 （LAGP）。
In the electrode with the composite structure, the lithium adsorption capacity reaches 133mg/g, the single-electrode lithium storage capacity reaches 1.4 kg (calculated according to metal lithium), and the cycle performance reaches 6000 times. In the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 8:1, the molar ratio of lithium ions/sodium ions is 7:1.
example 7
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 3, and the differences are as follows: the selective transmission layer is lithium lanthanum zirconium oxide (Li) with thickness of 40um (20 um coated on each surface and total thickness of 40um on both sides) 7 La 3 Zr 2 O 12 ，LLZO）。
In the composite structure electrode of the embodiment, the lithium adsorption capacity reaches 142mg/g, the single electrode lithium storage capacity reaches 1.4 kg (calculated according to metal lithium), and the cycle performance reaches 6000 times. In the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 20:1, the molar ratio of lithium ions/sodium ions is 1:1.
example 8
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 1, and the differences are as follows: the lithium storage layer is 5mm thick (2.5 m per side coating)m, total thickness of both sides 5 mm), and a 200um thick (100 um coated on each side, total thickness of both sides 200 um) Li as a selective transmission layer 4 Ti 5 O 12 。
The electrode with the composite structure can use the iron sheet as a negative electrode, utilizes the characteristic that the iron sheet is automatically dissolved in seawater, does not need to be electrified, and realizes the process of extracting lithium in seawater. In the electrode with the composite structure, the lithium adsorption capacity reaches 82mg/g, the single-electrode lithium storage capacity reaches 0.2 kg (calculated according to metal lithium), and the cycle performance reaches 6000 times.
Example 9
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 1, and the differences are as follows: the lithium storage layer is made of graphite with the thickness of 1mm (0.5 mm is coated on each surface, the total thickness of two sides is 1 mm), and the selective transmission layer is made of Li with the thickness of 100um (50 um is coated on each surface, 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, utilizes the characteristic that the iron sheet is automatically dissolved in seawater, does not need to be electrified, and realizes the process of extracting lithium in seawater. In the electrode with the composite structure of the embodiment, the lithium adsorption capacity reaches 82mg/g, the single-electrode lithium storage capacity reaches 0.05 kg (calculated according to metal lithium), and the cycle performance reaches 6000 times.
Example 10
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 1, and the differences are as follows: the lithium storage layer is made of 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 made of Li with the thickness of 80um (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, utilizes the characteristic that the iron sheet is automatically dissolved in seawater, does not need to be electrified, and realizes the process of extracting lithium in seawater. In the electrode with the composite structure of the embodiment, the lithium adsorption capacity reaches 85mg/g, the single electrode lithium storage capacity reaches 0.009 kg (calculated according to metal lithium), and the cycle performance reaches 6000 times.
Example 11
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 1, and the differences are as follows: the selectively permeable layer is Li 1-x FePO 4 （0<x≤1)。
The extraction effect of the electrode with the composite structure of the embodiment is basically the same as that of the embodiment 1, but the selected transmission layer material contains less lithium, and the cost is 30% lower than that of the embodiment 1.
Example 12
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 1, and the differences are as follows: the selectively permeable layer is Li 1-x Mn 2 O 4 （0<x≤1)。
The extraction effect of the electrode with the composite structure of the embodiment is basically the same as that of the embodiment 1, but the selected transmission layer material contains less lithium, and the cost is 40% lower than that of the embodiment 1.
Example 13
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 1, and the differences are as follows: the selectively permeable layer is Li 7-x Ti 5 O 12 （0<x≤4）。
The extraction effect of the electrode with the composite structure of the embodiment is basically the same as that of the embodiment 1, but the selected transmission layer material contains less lithium, and the cost is 20% lower than that of the embodiment 1.
Example 14
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 3, and the differences are as follows: the selective permeation layer is composed of two layers, the inner layer is LiFePO with the thickness of 150um (75 um is coated on each surface, and the total thickness of two sides is 150 um) 4 The outer layer is lithium lanthanum titanium oxide Li with the thickness of 40um (20 um is coated on each surface, and the total thickness of two sides is 40 um) 0.33 La 0.56 TiO 3 。
The extraction effect of lithium ions of the electrode with the composite structure of the embodiment is basically the same as that of the embodiment 3; in the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 40:1, the molar ratio of lithium ions/sodium ions is 20:1. this embodiment adopts two-layer different selective permeation layer material, and is better to the isolation effect of impurity sodium and magnesium.
Example 15
The electrode with the composite structure, the manufacturing method and the application of the electrode are basically the same as those of the embodiment 3, and the differences are as follows: the selective permeation layer is composed of two layers, the inner layer is LiFePO with the thickness of 80um (40 um is coated on each surface, and the total thickness of the two sides is 80 um) 4 The outer layer is LiCl 2Al (OH) with a thickness of 20um (10 um per side and a total thickness of 20um on both sides) 3 ·nH 2 O，。
The extraction effect of lithium ions of the electrode with the composite structure of the embodiment is basically the same as that of the embodiment 3; in the produced extracting solution, the molar ratio of lithium ions to magnesium ions is 30:1, the molar ratio of lithium ions/sodium ions is 20:1. in the embodiment, two layers of different selective permeation layer materials are adopted, so that the isolation effect on sodium and magnesium impurities is better; liCl.2Al (OH) 3 ·nH 2 The O coating also has better hydrophilicity, and is beneficial to the surface adsorption of lithium ions.
Claims (12)
1. The electrode with the composite structure is characterized by comprising a lithium storage layer and a selective permeation layer coated on the surface of the lithium storage layer;
the material of the lithium storage layer is one or more than two of a carbon material, a silicon-carbon material and a silicon-oxygen material;
the material of the selective transmission layer is lithium ion anode 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 of the materials; the Li 5+x La 3 M 2 O 12 M in (A) represents one or more of Nb, ta and Zr.
2. The composite structured electrode according to claim 1, further comprising a current collector; the lithium storage layer is coated on the surface of the current collector and positioned between the current collector and the selective permeation layer; the thickness of the current collector is 1 to 5mm; the single-side thickness of the lithium storage layer is 0.1 to 50mm; the thickness of the single surface of the selective permeation layer is 5 to 200um.
3. The composite-structured electrode according to claim 1 or 2, wherein the carbon material is one or more of graphite, hard carbon, soft carbon, and graphene.
4. The composite structured electrode of claim 1~3 wherein the material of the lithium storage layer is a fixed carbon content of 99.9% or greater; d50 granularity is 5.0-30.0 um max Less than or equal to 70um; graphite with the graphitization degree of more than or equal to 90 percent;
or the fixed carbon content is more than or equal to 99 percent; d50 granularity is 5.0-10.0 um max Less than or equal to 30um; the compacted density of the powder is more than or equal to 1.0g/cm 3 The hard carbon negative electrode of (1);
or 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 to 20um max Less than or equal to 40um; the compacted density is more than or equal to 1.0g/cm 3 The silicon oxide material SiO;
or the Si content is more than or equal to 2 percent, and the carbon content is less than or equal to 98 percent; d50 is 10 to 20um max Less than or equal to 32um; the compacted density is more than or equal to 1.0g/cm 3 The silicon carbon material SiC.
5. The composite structural electrode of claim 1~4 wherein 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 、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。
6. The electrode of claim 1~5 in which the selectively permeable layer is made of LiFePO with Li content 4.3 + 0.3%, fe content 34.0 + 2.0%, P content 19.5 + 1.5%, electron microscope average particle size less than 100nm, secondary agglomerate particle less than 30um 4 ；
Or the Mn content is 58 +/-2.0 percent, and the Li content is 4.2 +/-0.4 percent; d50 is 6 to 14um max LiMn less than or equal to 100um 2 O 4 ；
Or the content of Li is 7.0 +/-0.5 percent, the D50 is 4 to 25um max LiCoO less than or equal to 70um 2 ；
Or the content of Li is 7.0 +/-0.5 percent, the D50 is 4 to 25um 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 Li with Ti content more than or equal to 45%, li content 6.0 +/-1.0% and D50 of 0.5-10um 4 Ti 5 O 12 。
7. The composite structured electrode of any one of claims 1~6 wherein said permselective layer has a bi-or multi-layer structure; liFePO is preferably used as the inner layer 4 Double-layer structure of lithium lanthanum titanium oxide on outer layer or LiFePO on inner layer 4 Outer layer LiCl 2Al (OH) 3 ·nH 2 A double-layer structure of O.
8. A method of making an electrode for a composite structure according to any one of claims 1~7 comprising the steps of:
(1) Uniformly mixing a lithium ion storage material and a binder to form slurry, coating the slurry on a current collector, rolling or extruding and molding, and drying to obtain a pole piece or a pole rod containing a lithium storage layer;
(2) Carrying out surface roughening treatment on the pole piece or the pole rod containing the lithium storage layer;
(3) Uniformly mixing the lithium ion selective permeation material and the binder to form slurry, coating the slurry on a pole piece or a pole rod which is subjected to surface roughening treatment and contains a lithium storage layer, and drying to obtain an electrode with a composite structure;
in the step (3), the coating times are one or more than two; 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 to 600 ℃; in the step (1), the pressure of rolling or extrusion molding is 0.1 to 5MPa; in the step (2), performing surface roughening treatment to enable the surface roughness Ra to be 20 to 200um; in the step (3), the number of coating times is 3 to 30.
10. Use of an electrode of a composite structure according to any one of claims 1~7 or a method of making an electrode of a composite structure according to any one of claims 8~9 in an electrochemical device comprising the electrode of the composite structure as a positive electrode and a metal as a negative electrode; introducing a lithium-containing solution, and extracting lithium by metal dissolution self-discharge so that lithium ions are gradually adsorbed on the electrode with the composite structure;
or the electrode with the composite structure is taken as a cathode, and metal is taken as an anode to form an electrochemical device; and introducing a lithium-containing solution, extracting lithium at constant pressure, and gradually adsorbing lithium ions on the electrode with the composite structure.
11. The use of the composite-structured electrode according to claim 10, wherein the lithium ions in the composite-structured electrode having adsorbed lithium ions are released into the extraction liquid by:
the method A comprises the following steps:
using an electrode of a composite structure adsorbing lithium ions as an anode, fe 2+ The iron 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;
or the method B:
the electrode with the composite structure is used as a cathode, the electrode with the composite structure absorbing lithium ions is used as an anode, an anion exchange diaphragm 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 the lithium ions enter the electrolyte.
12. Use of an electrode of composite structure according to claim 10 or 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 solution; the content of chloride ions in the electrolyte is preferably 10 to 100g/l; the voltage of the constant-voltage lithium extraction is 0 to 2V; and stopping constant-voltage lithium extraction when the electrode adsorption saturation or the current is reduced to be below 0.05 mA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211474457.7A CN115679122B (en) | 2022-11-23 | 2022-11-23 | Electrode with composite structure and manufacturing method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211474457.7A CN115679122B (en) | 2022-11-23 | 2022-11-23 | Electrode with composite structure and manufacturing method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115679122A true CN115679122A (en) | 2023-02-03 |
| CN115679122B CN115679122B (en) | 2024-03-15 |
Family
ID=85055041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211474457.7A Active CN115679122B (en) | 2022-11-23 | 2022-11-23 | Electrode with composite structure and manufacturing method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115679122B (en) |
Citations (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040137326A1 (en) * | 2002-11-09 | 2004-07-15 | Munshi M. Zafar A. | Lithium ion battery and methods of manufacturing same |
| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene combination electrode material |
| US20120251877A1 (en) * | 2011-03-31 | 2012-10-04 | Dongguan Amperex Electronics Technology Limited | Secondary lithium ion battery |
| US20120321913A1 (en) * | 2010-02-26 | 2012-12-20 | Shanghai Aowei Technology Development Co., Ltd. | Manufacturing method for long-lived negative electrode and capacitor battery adopting the same |
| US20120328923A1 (en) * | 2011-04-13 | 2012-12-27 | Denki Kagaku Kogyo Kabushiki Kaisha | Electrode material for lithium secondary battery and lithium secondary battery |
| WO2013021299A1 (en) * | 2011-08-08 | 2013-02-14 | Basf Se | Electrochemical cells |
| CN103219168A (en) * | 2013-03-28 | 2013-07-24 | 合肥工业大学 | Li4Ti5O12/ grapheme composite electrode material and preparation method thereof |
| US20140322613A1 (en) * | 2013-04-26 | 2014-10-30 | Sumitomo Osaka Cement Co., Ltd. | Electrode material, electrode, and lithium ion battery |
| US20160118657A1 (en) * | 2013-06-04 | 2016-04-28 | Iishihara Sangyo Kaisha, Ltd. | Process for manufacturing lithium titanium oxides |
| US20160204424A1 (en) * | 2013-08-21 | 2016-07-14 | Hydro-Quebec | Positive electrode material for lithium secondary battery |
| CN106374081A (en) * | 2016-11-10 | 2017-02-01 | 厦门日臻动力电源科技有限公司 | High-capacity lithium ion battery negative electrode plate and preparation method thereof |
| CN107201452A (en) * | 2017-04-13 | 2017-09-26 | 河北工业大学 | One kind is based on LiMn2O4The method that electrode material carries lithium from lithium-containing solution |
| CN107680830A (en) * | 2017-08-21 | 2018-02-09 | 宁波中车新能源科技有限公司 | A kind of lithium titanate/charcoal combination electrode and its application |
| CN108269964A (en) * | 2017-12-27 | 2018-07-10 | 国联汽车动力电池研究院有限责任公司 | A kind of composite solid electrode and preparation method thereof |
| US20180287142A1 (en) * | 2017-04-03 | 2018-10-04 | Nanotek Instruments Inc. | Encapsulated Anode Active Material Particles, Lithium Secondary Batteries Containing Same, and Method of Manufacturing |
| US20180309118A1 (en) * | 2017-04-25 | 2018-10-25 | Toyota Jidosha Kabushiki Kaisha | Negative electrode active material particles for lithium ion secondary battery and method of producing the same |
| US20190044137A1 (en) * | 2017-08-01 | 2019-02-07 | Nanotek Instruments, Inc. | Hybrid lithium anode electrode layer and lithium-ion battery containing same |
| CN109440132A (en) * | 2018-10-17 | 2019-03-08 | 武汉大学 | A kind of flow-type electrochemistry proposes lithium system |
| CN111710874A (en) * | 2020-08-19 | 2020-09-25 | 广州纳诺新材料科技有限公司 | Solid-state lithium battery, composite negative electrode and preparation method of composite negative electrode |
| CN112164776A (en) * | 2020-09-16 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Composite coated all-solid-state battery positive electrode material, preparation method thereof and all-solid-state battery |
| CN112670449A (en) * | 2020-12-23 | 2021-04-16 | 蜂巢能源科技有限公司 | Silicon-carbon composite pole piece, preparation method and application thereof |
| CN112670516A (en) * | 2019-11-15 | 2021-04-16 | 华中科技大学 | Three-dimensional composite current collector and preparation method thereof |
| US20210194046A1 (en) * | 2017-11-09 | 2021-06-24 | Research Institute Of Industrial Science & Technology | All-solid-state battery, manufacturing method therefor, secondary battery comprising same and monolithic battery module comprising same |
| US20210210758A1 (en) * | 2018-05-24 | 2021-07-08 | Honda Motor Co., Ltd. | Composite particles, method for producing composite particles, lithium ion secondary battery electrode, and lithium ion secondary battery |
| CN113293290A (en) * | 2021-05-21 | 2021-08-24 | 江苏中南锂业有限公司 | Electrode material for lithium extraction in salt lake and preparation method and application thereof |
| CN113293289A (en) * | 2021-05-21 | 2021-08-24 | 江苏中南锂业有限公司 | Preparation method of hydrophilic lithium extraction electrode |
| CN114597351A (en) * | 2022-02-24 | 2022-06-07 | 天津力神电池股份有限公司 | Preparation method of composite electrode plate, composite electrode plate and lithium ion battery |
-
2022
- 2022-11-23 CN CN202211474457.7A patent/CN115679122B/en active Active
Patent Citations (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040137326A1 (en) * | 2002-11-09 | 2004-07-15 | Munshi M. Zafar A. | Lithium ion battery and methods of manufacturing same |
| US20120321913A1 (en) * | 2010-02-26 | 2012-12-20 | Shanghai Aowei Technology Development Co., Ltd. | Manufacturing method for long-lived negative electrode and capacitor battery adopting the same |
| CN101877405A (en) * | 2010-04-20 | 2010-11-03 | 华南理工大学 | Preparation method of lithium titanate-graphene combination electrode material |
| US20120251877A1 (en) * | 2011-03-31 | 2012-10-04 | Dongguan Amperex Electronics Technology Limited | Secondary lithium ion battery |
| US20120328923A1 (en) * | 2011-04-13 | 2012-12-27 | Denki Kagaku Kogyo Kabushiki Kaisha | Electrode material for lithium secondary battery and lithium secondary battery |
| CN102934266A (en) * | 2011-04-13 | 2013-02-13 | Sei株式会社 | Electrode material for lithium secondary battery and lithium secondary battery |
| WO2013021299A1 (en) * | 2011-08-08 | 2013-02-14 | Basf Se | Electrochemical cells |
| CN103219168A (en) * | 2013-03-28 | 2013-07-24 | 合肥工业大学 | Li4Ti5O12/ grapheme composite electrode material and preparation method thereof |
| US20140322613A1 (en) * | 2013-04-26 | 2014-10-30 | Sumitomo Osaka Cement Co., Ltd. | Electrode material, electrode, and lithium ion battery |
| US20160118657A1 (en) * | 2013-06-04 | 2016-04-28 | Iishihara Sangyo Kaisha, Ltd. | Process for manufacturing lithium titanium oxides |
| US20160204424A1 (en) * | 2013-08-21 | 2016-07-14 | Hydro-Quebec | Positive electrode material for lithium secondary battery |
| CN106374081A (en) * | 2016-11-10 | 2017-02-01 | 厦门日臻动力电源科技有限公司 | High-capacity lithium ion battery negative electrode plate and preparation method thereof |
| US20180287142A1 (en) * | 2017-04-03 | 2018-10-04 | Nanotek Instruments Inc. | Encapsulated Anode Active Material Particles, Lithium Secondary Batteries Containing Same, and Method of Manufacturing |
| CN107201452A (en) * | 2017-04-13 | 2017-09-26 | 河北工业大学 | One kind is based on LiMn2O4The method that electrode material carries lithium from lithium-containing solution |
| US20180309118A1 (en) * | 2017-04-25 | 2018-10-25 | Toyota Jidosha Kabushiki Kaisha | Negative electrode active material particles for lithium ion secondary battery and method of producing the same |
| US20190044137A1 (en) * | 2017-08-01 | 2019-02-07 | Nanotek Instruments, Inc. | Hybrid lithium anode electrode layer and lithium-ion battery containing same |
| CN107680830A (en) * | 2017-08-21 | 2018-02-09 | 宁波中车新能源科技有限公司 | A kind of lithium titanate/charcoal combination electrode and its application |
| US20210194046A1 (en) * | 2017-11-09 | 2021-06-24 | Research Institute Of Industrial Science & Technology | All-solid-state battery, manufacturing method therefor, secondary battery comprising same and monolithic battery module comprising same |
| CN108269964A (en) * | 2017-12-27 | 2018-07-10 | 国联汽车动力电池研究院有限责任公司 | A kind of composite solid electrode and preparation method thereof |
| US20210210758A1 (en) * | 2018-05-24 | 2021-07-08 | Honda Motor Co., Ltd. | Composite particles, method for producing composite particles, lithium ion secondary battery electrode, and lithium ion secondary battery |
| CN109440132A (en) * | 2018-10-17 | 2019-03-08 | 武汉大学 | A kind of flow-type electrochemistry proposes lithium system |
| CN112670516A (en) * | 2019-11-15 | 2021-04-16 | 华中科技大学 | Three-dimensional composite current collector and preparation method thereof |
| CN111710874A (en) * | 2020-08-19 | 2020-09-25 | 广州纳诺新材料科技有限公司 | Solid-state lithium battery, composite negative electrode and preparation method of composite negative electrode |
| CN112164776A (en) * | 2020-09-16 | 2021-01-01 | 合肥国轩高科动力能源有限公司 | Composite coated all-solid-state battery positive electrode material, preparation method thereof and all-solid-state battery |
| CN112670449A (en) * | 2020-12-23 | 2021-04-16 | 蜂巢能源科技有限公司 | Silicon-carbon composite pole piece, preparation method and application thereof |
| CN113293290A (en) * | 2021-05-21 | 2021-08-24 | 江苏中南锂业有限公司 | Electrode material for lithium extraction in salt lake and preparation method and application thereof |
| CN113293289A (en) * | 2021-05-21 | 2021-08-24 | 江苏中南锂业有限公司 | Preparation method of hydrophilic lithium extraction electrode |
| CN114597351A (en) * | 2022-02-24 | 2022-06-07 | 天津力神电池股份有限公司 | Preparation method of composite electrode plate, composite electrode plate and lithium ion battery |
Non-Patent Citations (2)
| Title |
|---|
| 李旺;刘佳丽;周兰;: "国内外钛酸锂负极材料改性研究动态与前沿", 钢铁钒钛, no. 04 * |
| 石颖;闻雷;吴敏杰;李峰;: "碳材料在钛酸锂负极材料中的应用", 化学进展, no. 01 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115679122B (en) | 2024-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110660961B (en) | Positive plate and lithium ion battery | |
| JP5223281B2 (en) | Lithium ion secondary battery or composite particle for positive electrode of lithium secondary battery, and lithium ion secondary battery or lithium secondary battery | |
| WO2020259436A1 (en) | Method for improving stability and processability of ternary positive electrode material | |
| CN108493442A (en) | A kind of ternary lithium ion battery | |
| CN111342031B (en) | Multi-element gradient composite high-first-efficiency lithium battery negative electrode material and preparation method thereof | |
| CN115763717A (en) | Sodium ion battery positive electrode material, preparation method thereof, sodium ion battery positive electrode piece and sodium ion battery | |
| CN112701281A (en) | Composite olivine structure positive electrode material and preparation method and application thereof | |
| CN114566646B (en) | Nickel-doped lithium iron manganese phosphate positive electrode material and preparation method and application thereof | |
| CN114142161B (en) | Preparation method of modified lithium ion battery diaphragm | |
| CN107681113B (en) | Positive plate, preparation method thereof and secondary battery | |
| CN113328086B (en) | Pyrophosphate composite material, preparation method and application thereof, and sodium ion battery | |
| JP2012033438A (en) | Cathode for lithium ion secondary battery and lithium ion secondary battery using the same | |
| CN114725346B (en) | Sodium ion battery positive electrode material, preparation method thereof and sodium ion battery | |
| CN116454283A (en) | Potassium ion battery positive electrode additive and preparation method and application thereof | |
| CN114864894B (en) | High-pressure-resistant coating modified lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN115679122B (en) | Electrode with composite structure and manufacturing method and application thereof | |
| CN109309228B (en) | Positive electrode active material, preparation method, positive electrode and high-specific-energy power battery | |
| CN215896448U (en) | Lithium cell supplementing structure and lithium ion battery | |
| CN105591151A (en) | Multiplying power type ternary battery and preparation method thereof | |
| CN115312711A (en) | Positive electrode composite material and preparation method and application thereof | |
| CN115304104A (en) | Manganese series lithium supplement additive and preparation method and application thereof | |
| CN114497463A (en) | Method for continuously supplementing lithium to negative electrode of lithium ion battery | |
| CN115621412A (en) | Lithium ion battery positive plate, preparation method and lithium ion battery | |
| CN110783544A (en) | Carbon nanotube coated H 3PO 4Modified lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN116544418B (en) | Lithium cobalt oxide positive electrode material, preparation method thereof and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |