CN115612850A - Method for recycling metal elements in waste battery anode material - Google Patents
Method for recycling metal elements in waste battery anode material Download PDFInfo
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- CN115612850A CN115612850A CN202211357606.1A CN202211357606A CN115612850A CN 115612850 A CN115612850 A CN 115612850A CN 202211357606 A CN202211357606 A CN 202211357606A CN 115612850 A CN115612850 A CN 115612850A
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- anode
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- catholyte
- electrolysis
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- 238000000034 method Methods 0.000 title claims abstract description 84
- 239000010405 anode material Substances 0.000 title claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 33
- 239000010926 waste battery Substances 0.000 title claims abstract description 33
- 239000007789 gas Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 50
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002699 waste material Substances 0.000 claims abstract description 42
- 230000002829 reductive effect Effects 0.000 claims abstract description 27
- 239000010406 cathode material Substances 0.000 claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 23
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract description 9
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 78
- 239000007774 positive electrode material Substances 0.000 claims description 75
- 238000006722 reduction reaction Methods 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 53
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 18
- 229910013716 LiNi Inorganic materials 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000004891 communication Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 159000000000 sodium salts Chemical class 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 150000002736 metal compounds Chemical group 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000002386 leaching Methods 0.000 abstract description 76
- 230000009467 reduction Effects 0.000 abstract description 45
- 239000000463 material Substances 0.000 abstract description 31
- 230000008569 process Effects 0.000 abstract description 23
- 238000011084 recovery Methods 0.000 abstract description 13
- 239000011572 manganese Substances 0.000 description 56
- 210000004027 cell Anatomy 0.000 description 39
- 238000002474 experimental method Methods 0.000 description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 229910052744 lithium Inorganic materials 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229910012820 LiCoO Inorganic materials 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910018661 Ni(OH) Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000009854 hydrometallurgy Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- -1 nickel cobalt aluminum Chemical compound 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
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- 230000000694 effects Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 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
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910013210 LiNiMnCoO Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/081—Supplying products to non-electrochemical reactors that are combined with the electrochemical cell, e.g. Sabatier reactor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to the field of battery anode material recovery, in particular to a method for recycling metal elements in waste battery anode materials. The method comprises the following steps: 1) Providing waste cathode materials; waste anode material is put in reducing gasIntermediate calcination to provide a reductive reaction product; 2) Providing an electrolytic system; 3) Reacting the reductive reaction product of step 1) with the electrolyzed H in the anolyte + Reacting to provide transition metal element ions and/or alkali metal ions; 4) So that the transition metal ions are diffused into the catholyte and are reacted with OH ‑ Reacting to provide a hydroxide precipitate of the transition metal element. The invention adopts a high-temperature reduction and electrolytic water combined process, and the leaching efficiency of each element of the material after hydrogen reduction treatment is greatly improved. The hydrogen generated by electrolyzing water can be used as the gas for reducing the anode material again, and the closed loop of the hydrogen is realized.
Description
Technical Field
The invention relates to the technical field of recycling of battery anode materials, in particular to a method for recycling metal elements in waste battery anode materials.
Background
Electrochemical energy storage cells are used in a wide variety of applications in today's society. Since the 90 s of the 20 th century, lithium ion batteries have been widely used in the fields of mobile phones, cameras, notebook computers, electric vehicles, and the like, owing to their outstanding advantages of high energy density, long storage life, small volume, light weight, and the like. The quality of the lithium ion battery anode material directly determines various performances of the battery product. Common positive electrode materials for lithium ion batteries include lithium cobaltate (LiCoO) 2 ) Lithium manganate (LiMn) 2 O 4 ) Lithium iron phosphate (LiFePO) 4 ) Nickel cobalt manganese ternary material (LiNi) x Co y Mn 1-x-y O 2 ) And nickel cobalt aluminum ternary materials ((LiNi) x Co y Al 1-x- y O 2 ). However, in the last decade, with the vigorous development of the smart phone market and the electric automobile market, most lithium ion battery raw materials face the problems of supply shortage and price rise. In addition, if the used waste lithium ion battery is not treated properly, toxic heavy metals such as cobalt, nickel, manganese and the like can permeate into underground water and soil, and serious environmental pollution is caused. The positive electrode material of the sodium ion battery, which is still in the development stage, also contains similar metal elements, and is worthy of recycling in the future. In addition, the positive electrode material MnO of the zinc-manganese battery 2 The manganese element in the manganese alloy also has recovery value. How to efficiently recycle the anode material of the waste battery, relieve the resource pressure and reduce the environmental pollution to the maximum extent becomes an urgent need.
At present, the recovery of the anode material of the lithium ion battery is mainly divided into three types: direct recovery process, hydrometallurgical process and fireA hydrometallurgical process. The direct recovery method has lower cost, but has little effect on batteries with high anode and cathode aging degrees. Pyrometallurgical processes are relatively high in energy consumption and cost, and require the investment of large exhaust gas treatment systems. In contrast, hydrometallurgy has gained much attention due to its advantages of high recovery efficiency, high element selectivity, and low energy consumption. However, co in high valence state in lithium cobaltate, lithium manganate and nickel cobalt manganese ternary cathode material 3+ And Mn 4+ Is difficult to be completely dissolved by acid, and generally has low leaching efficiency. In order to improve the leaching efficiency, a reducing agent is often added into the acid liquor to reduce the high-valence metal elements into lower-valence metal elements. The process consumes a large amount of acid, alkali and reducing agent, increases the cost, and also discharges a large amount of waste liquid, thereby bringing about serious environmental pollution. Therefore, the efficient and environment-friendly recovery treatment process for the lithium ion battery anode material is developed, and great economic and environment-friendly benefits are achieved.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to provide a method for recycling metal elements in a positive electrode material of a waste battery, which combines a high-temperature reduction method and an electrolytic water method, so as to realize the recycling of hydrogen, effectively improve the leaching rate of the metal elements, and avoid the generation of waste liquid. The invention realizes the effective recovery of the anode material of the waste battery, thereby solving the problems in the prior art.
The invention is realized by the following technical scheme:
the invention provides a method for recycling metal elements in a waste battery anode material on the one hand, which comprises the following steps:
1) Providing waste anode materials; calcining the spent positive electrode material in a reducing gas to provide a reducing reaction product;
2) Providing an electrolytic water system comprising an anode and a cathode, the anode comprising an anolyte, the anolyte comprising water, the anolyte being electrolyzed to provide O 2 And H + The cathode includes a catholyte, the catholyte including water, the catholyte being electrolyzed to provide H 2 And OH - (ii) a Said H 2 Recycled as reducing gas for use in step 1);
3) Reacting the reductive reaction product of step 1) with the H electrolyzed in the anolyte of step 2) + Reacting to provide ions of a transition metal element and/or ions of an alkali metal;
4) Diffusing the transition metal ions provided in the step 3) into the catholyte in the step 2) to react with OH - Reacting to provide a hydroxide precipitate of the transition metal element.
In another aspect, the present invention provides an electrolysis system comprising a reduction reaction apparatus and an electrolysis apparatus; the reduction reaction device comprises a reaction cavity; the electrolysis device comprises an anode and a cathode, and the anode and the cathode are respectively connected with a power supply; also comprises a gas communicating pipeline; the cathode is communicated with the reaction cavity through a gas communication pipeline.
Compared with the prior art, the invention has the beneficial effects that:
the method and the device provided by the invention adopt a combined process of high-temperature reduction and electrolytic water. The method comprises the steps of reducing the anode material into metal oxide which is easy to dissolve in acid through hydrogen, and efficiently recovering metal elements in the anode material by utilizing the pH gradient generated by electrolyzed water. In addition, hydrogen generated by electrolyzing water can be used as gas for reducing the cathode material again, and closed loop of the hydrogen is realized. Compared with a pure acid leaching anode material, the leaching efficiency of each element of the material subjected to hydrogen reduction treatment is obviously improved. The method avoids using a large amount of chemicals such as acid, alkali, reducing agent and the like, has low cost and simple process, avoids generating waste liquid, is environment-friendly and is expected to be industrially utilized on a large scale.
Drawings
FIG. 1 is a process diagram of the present invention, which takes the recycling of nickel cobalt lithium manganate ternary positive electrode material (NCM) of waste lithium ion battery as an example.
FIG. 2 is a diagram of the apparatus of the present invention.
FIG. 3 shows LiNi, a positive electrode material in example 1 0.5 Co 0.2 Mn 0.3 O 2 At 5% of H 2 -95% in Ar at 300 ℃X-ray diffraction pattern of the product after 135 minutes from the start.
FIG. 4 shows LiNi, a positive electrode material in example 3 0.5 Co 0.2 Mn 0.3 O 2 At 5% of H 2 -95% X-ray diffraction pattern of the product after reduction in ar at 300 ℃ for 180 minutes.
FIG. 5 shows LiMn as a positive electrode material in example 5 2 O 4 At 5% of H 2 -95% X-ray diffraction pattern of the product after reduction in ar at 850 ℃ for 150 minutes.
FIG. 6 shows LiCoO, a positive electrode material in example 6 2 At 5% of H 2 -95% X-ray diffraction pattern of the product after reduction in Ar at 375 ℃ for 50 minutes.
FIG. 7 shows MnO as a positive electrode material in example 8 2 At 5% of H 2 -95% X-ray diffraction pattern of the product after reduction in Ar at 850 ℃ for 150 minutes.
Element numbers in the figures:
1. electrolysis device
11. Power supply
12. Anode
121. Anode body
122. Anode electrolysis chamber
13. Cathode electrode
131. Cathode body
132. Cathode electrolysis chamber
14. Communicating chamber
15. Oxygen outlet
16. Hydrogen outlet
17. Diaphragm
18. Sample bottle
2. Reduction reaction device
21. Reaction chamber
3. Gas communication pipeline
Detailed Description
The following detailed description specifically discloses an embodiment of the method for recycling metal elements in the positive electrode material of the waste battery.
As disclosed herein, a "range" is defined in terms of lower and upper limits, with a given range being defined by the selection of one lower limit and one upper limit, which define the boundaries of the particular range. Ranges defined in this manner may or may not include the stated limits and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps 1) and 2), meaning that the method may comprise steps 1) and 2) performed sequentially, and may also comprise steps 2) and 1) performed sequentially.
In order to improve the leaching efficiency of elements and simplify the recovery process of metal elements in the battery anode material, the inventor of the invention discovers a method for recovering metal elements in the waste battery anode material through a great deal of research, and the invention utilizes the combined process of high-temperature reduction and acid leaching (acidic solution can be provided by electrolyzed water), firstly uses reducing gas (such as hydrogen) to reduce transition metal elements in the anode material into low state under the high-temperature condition, and then uses an H-shaped electrolytic tank filled with neutral aqueous solution to leach transition metal elements from the reduced product in an anode chamberMetallic elements (e.g. Ni) 2+ 、Co 2+ 、Mn 2+ ) And Li + And the transition metal elements are precipitated in the form of hydroxide in the cathode chamber and are easy to separate. On this basis, the present application has been completed.
The invention provides a method for recycling metal elements in a positive electrode material of a waste battery, which comprises the following steps:
1) Providing waste anode materials; calcining the spent positive electrode material in a reducing gas to provide a reducing reaction product;
2) Providing an electrolytic water system comprising an anode and a cathode, the anode comprising an anolyte, the anolyte comprising water, the anolyte being electrolyzed to provide O 2 And H + The cathode includes a catholyte, the catholyte including water, the catholyte being electrolyzed to provide H 2 And OH - (ii) a Said H 2 Recycled as reducing gas for use in step 1);
3) Reacting the reductive reaction product of step 1) with the H electrolyzed in the anolyte of step 2) + Reacting to provide ions of a transition metal element and/or ions of an alkali metal;
4) Diffusing the transition metal ions provided in the step 3) into the catholyte in the step 2) to react with OH - Reacting to provide a hydroxide precipitate of the transition metal element.
In the method for recycling the metal elements in the anode material of the waste battery, step 1) is to provide the waste anode material, wherein the anode material of the battery is usually a complex metal oxide. Specifically, the method comprises the following steps: in step 1), the waste positive electrode material may be selected from positive electrode materials of lithium ion batteries or other batteries. Other batteries may be, for example, sodium ion batteries, zinc ion batteries. The zinc ion battery may be, for example, a zinc-manganese battery. In some embodiments, the positive electrode material of the spent lithium ion battery is selected from LiCoO 2 、LiNi x Co y Mn 1-x-y O 2 、LiNi x Co y Al 1-x-y O 2 、LiNiO 2 、LiMn 2 O 4 、NaCoO 2 、NaNi x Co y Mn 1-x-y O 2 、MnO 2 And the like. The anode material of the waste sodium-ion battery is selected from NaCoO 2 、NaNi x Co y Mn 1-x-y O 2 And the like. The anode material of the zinc-manganese battery is selected from MnO 2 . Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, and x + y + z =1. Preferably, x is selected from 0.2 to 0.95; y is selected from 0.01 to 0.3.
In the invention, the waste positive electrode material can be obtained by pretreating the waste battery. Taking the recovered nickel-cobalt-manganese ternary material as an example, the pretreatment steps are as follows:
a) And (3) completely discharging the waste battery in NaCl for a period of time, washing with deionized water, and drying at room temperature.
b) The cells were manually disassembled in a fume hood to obtain the pole pieces containing aluminum foil and positive electrode material.
c) And (3) placing the positive plate in a tube furnace, roasting in vacuum, and removing the electrolyte and the binder. After that, the positive electrode material was peeled off from the aluminum foil for use.
d) And ball-milling the stripped positive electrode material in a ball mill, and then drying.
e) Adding deionized water, and separating most of graphite and the anode material by a suspension method.
f) The positive electrode material was dried and used for the next calcination experiment.
In step 1), the step of calcining the waste cathode material in reducing gas to provide a reducing reaction product is a high-temperature reduction step, and the reducing gas is selected from hydrogen or a mixed gas of hydrogen and inert gas. When the reducing gas is selected from a mixture of hydrogen and an inert gas, the two gases may be mixed in a certain molar ratio. Note that the inert gas does not participate in the reaction. The reason for adding the inert gas is to reduce the risk of the reaction. For example, the molar ratio of hydrogen to inert gas is 2 to 8:92 to 98. The inert gas is selected from argon and/or nitrogen. Preferably 5% of H 2 -95% Ar (mol)Mole fraction) of the mixed gas. The temperature of the reduction reaction may be, for example, 300 to 900 ℃,300 to 600 ℃, 600 to 900 ℃,300 to 400 ℃, 400 to 500 ℃, 500 to 600 ℃, 600 to 700 ℃, 700 to 800 ℃, or 800 to 900 ℃. The time for the reduction reaction is, for example, 1 to 10h,10 to 24h,1 to 5h,5 to 10h,10 to 15h,15 to 20h, or 20 to 24h.
In the step 1), the reaction temperature and the reaction time are reasonably controlled, so that the obtained reductive reaction product is mainly a metal compound instead of a metal simple substance. The reductive reaction product is a metal compound; the metal compound is one or a mixture of more of LiOH, naOH, niO, coO and MnO. For example, the nickel cobalt lithium manganate ternary material is recycled, and the metal compound is a mixture of LiOH, niO, coO and MnO. For example, recovery of NaCoO 2 And the metal compound is a mixture of NaOH and CoO. If other positive electrode materials are to be recycled, e.g. LiMn 2 O 4 The metal compound is then a mixture of LiOH and MnO. More for example, if MnO is recovered 2 The reduced metal compound is MnO. The transition metal element in a high valence state is changed into a lower valence state by a reduction reaction. Taking waste anode material as LiNi 0.5 Co 0.2 Mn 0.3 O 2 The reducing gas is H 2 For example, the reaction formula is: 2LiNi 0.5 Co 0.2 Mn 0.3 O 2 +H 2 =2LiOH+NiO 0.4CoO +0.6MnO. The valence states of transition metal elements Ni, co and Mn in the reduction product are all reduced to +2. The reaction can be carried out in a reduction reaction apparatus as shown in FIG. 2.
In the method for recycling the metal elements in the anode material of the waste battery, provided by the invention, in the steps 2) -4), the reduction reaction product (namely, metal compound) obtained in the step 1) is taken as a raw material and is put into an anode chamber of an H-shaped electrolytic tank. Neutral electrolyzed water is generated in the H-shaped electrolytic cell, and oxygen evolution reaction (H) is generated at the anode of the anode chamber 2 O＝1/2O 2 +2H + +2e - ) Can provide hydrogen ions (H) for leaching of metal compounds + ) (ii) a Cathodic hydrogen evolution reduction (H) of the cathode chamber 2 O+e - ＝1/2H 2 +OH - ) Not only generates high-value hydrogen gas, but also generates hydroxyl ions (OH) - ) The transition metal ions (e.g., co) diffused from the anode can be used 2+ 、Mn 2+ 、Ni 2+ ) A precipitate forms (e.g. Co (OH) 2 、Mn(OH) 2 、Ni(OH) 2 ). In addition, leached Li + Can be replaced by Li 2 CO 3 Is recovered. Then, the deposit in the cathode chamber is collected and utilized, and Li 2 CO 3 After being mixed according to a certain proportion, the mixture is roasted in the air at high temperature, and the anode material can be regenerated. The following describes in detail the steps 2) to 4).
In the method for recycling the metal elements in the anode materials of the waste batteries, step 2) is to provide an electrolytic water system, wherein the electrolytic water system comprises an anode and a cathode, the anode comprises an anolyte, the anolyte comprises water, and the anolyte is electrolyzed to provide O 2 And H + The cathode includes a catholyte, the catholyte including water, the catholyte being electrolyzed to provide H 2 And OH - (ii) a Said H 2 Recycled as reducing gas for use in step 1). In addition, the anode generates oxygen, which has economic value and can be collected.
In the step 2), the electrolyzed neutral water can not only generate hydrogen and oxygen, but also generate an acidic solution environment in the anode chamber and an alkaline solution environment in the cathode chamber. Specifically, the anode may be made of platinum wire, for example. The cathode may be made of, for example, a platinum wire or a platinum-plated titanium rod. The anolyte is selected from sodium salt aqueous solution electrolyte; the sodium salt is selected from Na 2 SO 4 、NaNO 3 And NaClO 4 One or more of the above. The catholyte is selected from a sodium salt aqueous electrolyte; the sodium salt is selected from Na 2 SO 4 、NaNO 3 And NaClO 4 One or more of the above.
In the method for recycling metal elements in the anode material of the waste battery, which is provided by the invention, in the step 3), the metal elements in the step 1) are recycledWith H electrolyzed in the anolyte of step 2) + React to provide transition metal element ions (in some embodiments, the transition metal element ions may be, for example, ni) 2+ 、Co 2+ 、Mn 2+ One or a combination of more of (a) and alkali metal ions (Li) and + 、Na + ) And the like. Wherein a half-reaction takes place on the anode side: h 2 O＝1/2O 2 (g)+H + +2e - . Usually accompanied by oxygen (O) 2 ) With hydrogen ions (H) at the anode + ) Continued production, such that the pH near the anode is lowered, e.g., to a pH of 3 to 3.5, can gradually dissolve the positive electrode material, e.g., liCoO 2 、LiMn 2 O 4 、LiNiO 2 、LiNi x Co y Mn 1-x-y O 2 . Specifically, liCoO 2 Reacts with acid and generates Co after dissolution 2+ And Li + Etc. to form Co 2+ 、Li + Dissolved in an aqueous solution. LiMn 2 O 4 React with acid and generate Mn after dissolution 2+ And Li + Etc. to produce Mn 2+ 、Li + Dissolved in an aqueous solution. LiNi x Co y Mn 1-x-y O 2 Reacts with acid and generates Co after dissolution 2+ 、Ni 2+ 、Mn 2+ And Li + Etc. to form Co 2+ 、Ni 2+ 、Mn 2+ 、Li + Dissolved in an aqueous solution. The reaction may be carried out in an H-type electrolytic cell as shown in fig. 2. The anode material obtained in the step 1), such as powder, is placed in an anode electrolysis chamber of an H-shaped electrolytic cell. The powder with density higher than that of water sinks to the bottom of the anode electrolysis chamber.
In the method for recycling the metal elements in the anode material of the waste battery, provided by the invention, in the step 4), the transition metal element ions (such as Co) provided in the step 3) are enabled to be in a transition state 2+ 、Ni 2+ 、Mn 2+ ) Diffusing into the catholyte and OH in the step 2) - Reacting to provide a hydroxide precipitate of the transition metal element (corresponding to the formation of, e.g., co (OH) 2 、Ni(OH) 2 、Mn(OH) 2 One or a combination of more of the precipitates). Wherein a half-reaction takes place on the cathode side: h 2 O+e - ＝1/2H 2 (g)+OH - . With hydrogen (H) 2 ) With the generation of OH - Continued generation causes the pH near the cathode to rise, e.g., to a pH of 10.5 to 11, while Co 2+ 、Ni 2+ 、Mn 2+ And Li + Etc. may diffuse from the anolyte on the anode side to the catholyte on the cathode side. Since the solution on the cathode side is alkaline, the pH value is higher, co 2+ 、Ni 2+ 、Mn 2+ Diffuse to the cathode and hydroxide ion (OH) - ) Combined to form a precipitate (e.g. Co (OH) 2 、Ni(OH) 2 、Mn(OH) 2 ) Filtered and collected, for example the precipitate obtained on the cathode side can be separated from the electrolytic cell, rinsed with deionized water and dried, more for example in an oven, to obtain Co (OH) 2 、Ni(OH) 2 、MnO x (manganese oxide) powder, thereby realizing the extraction of the valuable transition metal elements of cobalt, nickel and manganese. Lithium ion (Li) leached from reductive reaction products during electrolysis + ) And also gradually diffuse from the anolyte to the catholyte. Since LiOH has a high solubility in water, liOH does not form a precipitate. In addition, the cathode produces hydrogen, which is of economic value and can be collected for recycling in step 1). The reaction may be carried out in an H-type electrolytic cell as shown in fig. 2.
In the method for recycling the metal elements in the anode material of the waste battery, the reaction temperature of the anolyte and/or the catholyte is 20-30 ℃;30 to 40 ℃;40 to 50 ℃; 50-60 ℃;60 to 70 ℃;70 to 80 ℃;80 to 95 ℃;80 to 85 ℃; 85-90 ℃; or 20 to 95 ℃. For example, the H-type electrolytic cell may be adjusted to 80 to 95 ℃.
In the method for recycling the metal elements in the anode material of the waste battery, the electrolytic voltage of the anolyte and/or the catholyte is 3-5V, 3-4V or 4-5V in the electrolytic process. The electrolysis time of the anode electrolysis water and/or the cathode electrolysis water is 12-24h, 12-14h, 14-20 h or 20-24 h.
In the method for recycling metal elements in the anode material of the waste battery provided by the invention, for example, lithium ions in the aqueous solution obtained in the step 4) can be added with soluble carbonate solution such as (Na) 2 CO 3 Solutions, more e.g. saturated Na 2 CO 3 Solution), and gradually Li by volatilization of water 2 CO 3 Precipitating out, then filtering and drying Li 2 CO 3 Precipitate and collect. In some embodiments, the hydroxide precipitate of the transition metal element in step 4) may be separated from the catholyte prior to addition of the carbonate solution to the electrolyte to provide Li + Reacts with carbonate ions to generate Li2CO3 precipitate.
In the method for recycling the metal elements in the anode material of the waste battery, provided by the invention, hydroxide precipitates and Li of the transition metal elements are collected 2 CO 3 Calcined to provide regenerated positive electrode material, which may be, for example, liCoO 2 Electrode material and LiMn 2 O 4 Electrode material and LiNiMnCoO 2 Electrode materials, and the like. Wherein, for example, the temperature of calcination is 850 to 900 ℃. The roasting time is 4 to 12 hours, 4 to 8 hours, or 8 to 12 hours. More specifically, in forming LiCoO 2 Electrode material, co (OH) 2 Precipitation and Li 2 CO 3 The mol ratio of the precipitate is 0.9-1: 1 to 1.1.
The invention provides an electrolysis system used in a method for recycling metal elements in a positive electrode material of a waste battery. As shown in fig. 1, the electrolysis system comprises: comprises a reduction reaction device 2 and an electrolysis device 1; the reduction reaction device comprises a reaction cavity 21; the electrolysis device comprises an anode 12 and a cathode 13, wherein the anode 12 and the cathode 13 are respectively connected with a power supply 11; also comprises a gas communicating pipeline 3; the cathode 13 and the reaction chamber 21 are communicated through a gas communication pipeline 3. In the electrolysis system of the present invention, the power source 11 is not limited.
In the electrolysis system provided by the present invention, the reduction reaction apparatus may be, for example, a tube furnace.
In the electrolysis system provided by the present invention, as shown in fig. 2, the anode 12 includes an anode body 121 and an anolyte chamber 122, an anolyte is disposed in the anolyte chamber 122, and the anode body 121 is in contact with the anolyte. The anode body 121 is filled with an anolyte selected from the group consisting of a sodium salt aqueous electrolyte; the sodium salt is selected from Na 2 SO 4 、NaNO 3 And NaClO 4 The solubility of the sodium salt aqueous solution electrolyte is 0.5-1.5M. The reaction at the anode is: h 2 O＝1/2O 2 (g)+H + +2e - . The bottom of the anode electrolysis chamber 122 is provided with a sample tube 18, and the sample tube 18 is used for containing the reductive reaction product obtained in the reductive reaction device.
Further, the anode body 121 includes an anode material thereon, and the anode material includes a platinum wire.
Further, the anode body 121 is connected to a positive electrode of the power source 11.
In the electrolysis system provided by the invention, as shown in fig. 1, the cathode 13 comprises a cathode body 131 and a cathode electrolysis chamber 132, the cathode electrolysis chamber 132 is provided with a catholyte, and the cathode body 131 is in contact with the catholyte. In one embodiment, the catholyte is an aqueous sodium salt electrolyte; the sodium salt is selected from Na 2 SO 4 、NaNO 3 And NaClO 4 Or a combination of one or more thereof. The solubility of the sodium salt aqueous solution electrolyte is 0.5-1.5M, 0.5-1.0M, or 1.0-1.5M. The reaction at the cathode is: h 2 O+e - ＝1/2H 2 (g)+OH - 。
Further, the cathode body 131 includes a cathode material including a platinum wire or a platinum-plated titanium rod.
Further, the cathode body 131 is connected with the negative electrode of the power supply 11;
in the electrolysis system provided by the invention, in order to reduce the liquid convection, a diaphragm 17, such as filter paper, cloth and the like, is arranged between the anode electrolysis chamber 122 and the cathode electrolysis chamber 132 of the electrolysis system. The anolyte and catholyte are separated by a separator 17. In a specific embodiment, the electrolysis system is an H-type electrolytic cell, and includes an anode body 121 and a cathode body 131 respectively disposed on two sides of the H-type electrolytic cell, an anode electrolysis chamber 122 and a cathode electrolysis chamber 132, and a communication chamber 144 for communicating the anode electrolysis chamber 122 and the cathode electrolysis chamber 132, wherein the diaphragms 17 are respectively disposed on two sides of the communication chamber 144. The communication chamber 144 is generally located intermediate the anolyte chamber 122 and the catholyte chamber 132. The separator 17 on both sides may allow ions to pass through to the cathode, but not positive electrode materials such as positive electrode powder.
The electrolysis system provided by the invention further comprises an oxygen outlet 15 communicated with the anode electrolysis chamber 122. For the passage of oxygen and for the collection of oxygen by external collection means.
The present invention provides an electrolysis system that further includes a hydrogen outlet 16 in communication with the catholyte chamber 132. For the passage of hydrogen and collecting the hydrogen by an external collecting device. The hydrogen outlet 16 is in communication with a gas communication conduit. The hydrogen may be recycled to the reduction reaction apparatus.
Compared with the prior art, the invention has the following advantages:
the method and the device provided by the invention adopt a combined process of high-temperature reduction and electrolytic water. The anode material is reduced into metal oxide which is easy to dissolve in acid through hydrogen, and then the metal element in the anode material is recovered by utilizing the pH value gradient generated by electrolyzed water. In addition, hydrogen generated by electrolyzing water can be used as gas for reducing the cathode material again, and closed loop is realized. Compared with a pure acid leaching anode material, the leaching efficiency of each element of the material subjected to hydrogen reduction treatment is greatly improved. The method avoids using a large amount of chemicals such as acid, alkali, reducing agent and the like, has low cost and simple process, is environment-friendly, and is expected to be industrially utilized on a large scale.
Compared with the H-type electrolytic cell only using neutral aqueous solution, the invention is a combined process of high-temperature reduction and electrolytic water, firstly reduces the waste anode material at high temperature, reduces the high-valence transition metal element in the waste anode material to low-valence state, and greatly improves the leaching efficiency of the next anode chamber of the H-type electrolytic cell.
The present invention is also distinguished from conventional hydrometallurgy. In order to effectively leach transition metal elements, the traditional hydrometallurgy generally adds a high-value reducing agent (such as H) in acid liquor 2 O 2 ). In contrast, the invention can directly use the hydrogen generated by electrolyzing water as the reducing gas of the anode material, thereby realizing the recycling of the hydrogen; in addition, the acid-base gradient generated by electrolyzing neutral water can effectively leach metal elements from reduction products and can precipitate transition metal element ions in the form of hydroxide. Therefore, the process of the invention does not consume a large amount of additional acid, alkali and reducing agent, and does not generate waste liquid, thereby being an environment-friendly battery cathode material recovery process.
The following examples are provided to further illustrate the advantageous effects of the present invention.
In order to make the purpose, technical solutions and advantageous technical effects of the present invention clearer, the present invention is described in further detail below with reference to examples. However, it should be understood that the embodiments of the present invention are only for explaining the present invention and not for limiting the present invention, and the embodiments of the present invention are not limited to the embodiments given in the specification. The examples were made under conventional conditions, or conditions recommended by the material suppliers, without specifying specific experimental conditions or operating conditions.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it should also be understood that a combinational connection relationship between one or more devices/apparatuses mentioned in the present invention does not exclude that other devices/apparatuses may also be present before or after the combinational device/apparatus or that other devices/apparatuses may also be interposed between the two devices/apparatuses explicitly mentioned, unless otherwise stated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
In the following examples, reagents, materials and instruments used are commercially available unless otherwise specified.
Examples
The invention provides a high-temperature reduction and electrolytic water combined process, which takes the recovery of metal elements in a nickel-cobalt-manganese ternary material as an example, and comprises the following steps:
step 1: pretreating the waste lithium ion battery material
1) The waste battery is completely discharged in 1mol/L NaCl for 24 hours, washed by deionized water and dried at room temperature.
2) The cell was manually disassembled in a fume hood to obtain the pole pieces containing aluminum foil and positive electrode material.
3) And (3) placing the positive plate in a tube furnace, vacuum-firing at 300 ℃ for 3 hours, and removing the electrolyte and the binder. After that, the positive electrode material was peeled off from the aluminum foil for use.
4) The stripped positive electrode material was ball-milled in a ball mill at 500 revolutions per minute for two hours and then dried at a temperature of 90 c for six hours.
5) Adding deionized water, and separating most of graphite and the anode material by a suspension method.
6) The positive electrode material was dried and used for the next calcination experiment.
And 2, step: hydrogen-reducing cathode material
1) 2g of nickel-cobalt-manganese ternary material is weighed in a corundum crucible and put into a tube furnace.
2) Argon gas is introduced into the tube furnace, and the temperature is raised at a speed of 5 ℃/min.
3) And when the tube furnace reaches the target temperature, closing the argon. Opening 5% H 2 The flow rate of the mixed gas/Ar is 150cm 3 And/min, calcining for different times, and observing phase compositions.
4) After the set reduction time has ended, 5% are switched off 2 And (4) opening argon gas for purging and cooling the mixed gas/Ar.
And step 3: assembled electrolytic cell
1) And filter paper is placed at the joint of each chamber and the communicating pipe so as to slow down the convection of the solution. Subsequently, na is added 2 SO 4 And adding the electrolyte into an H-shaped electrolytic cell.
2) An electrode is inserted. Platinum wires (diameter 1 mm) were used for the anode, and platinum-plated titanium rods (diameter 6 mm) were used for the cathode.
3) And (3) putting the reduced anode material into a small crucible, adding electrolyte into the small crucible, putting the small crucible into the anode side of an H-shaped electrolytic cell after the material is settled and stabilized, and adding the electrolyte. And (5) raising the temperature.
And 4, step 4: electrolytic water in H-shaped electrolytic cell
1) Applying 3.5V voltage, and electrolyzing for 6-24 h. The experimental phenomena included:
a) During electrolysis, bubbles are generated at the electrodes of both the anode and the cathode. The anode compartment is acidic and the cathode compartment is basic.
b) The material placed in the anode cavity can leach Co in an acid environment 2+ ，Mn 2+ ，Ni 2+ And Li + And will diffuse to the cathode chamber.
c) Co diffused from anode 2+ ，Mn 2+ ，Ni 2+ Will contact the OH of the cathode chamber - React to produce Co (OH) 2 ，Mn(OH) 2 ，Ni(OH) 2 And (4) precipitating. Since LiOH has a high solubility in water, liOH does not form a precipitate.
d) The oxygen produced at the anode can be collected as a valuable by-product.
e) The hydrogen generated by the cathode can be recycled as the gas of the reduction reaction to form a closed-loop lithium ion battery recovery process.
And 5: regeneration of positive electrode material
1) And after the electrolysis is finished, collecting the precipitate in the cathode chamber. First dissolving in dilute sulfuric acid, then adding NiSO 4 ，CoSO 4 And MnSO 4 So that the ratio of Ni to Co to Mn is adjusted to 5. Finally, an excess NaOH solution is added to fully precipitate transition metal ions.
2) According to the followingLi/(Ni + Co + Mn) =1.05 molar ratio is added with Li 2 CO 3 Grinding, and then calcining the mixture in a muffle furnace at 950 ℃ for 10 hours to obtain the regenerated nickel-cobalt-manganese ternary material.
Example 1:
LiNi which is a waste lithium ion battery cathode material is recycled by adopting a high-temperature hydrogen reduction and electrolytic water combined process 0.5 Co 0.2 Mn 0.3 O 2 The method comprises the following steps:
step 1: pretreating the waste lithium ion battery material
1) The waste battery is completely discharged in 1mol/L NaCl for 24 hours, washed by deionized water and dried at room temperature.
2) The cells were manually disassembled in a fume hood to obtain the pole pieces containing aluminum foil and positive electrode material.
3) And (3) placing the positive plate in a tube furnace, vacuum-firing at 300 ℃ for 3 hours, and removing the electrolyte and the binder. After that, the positive electrode material was peeled off from the aluminum foil for use.
4) The stripped positive electrode material was ball-milled in a ball mill at 500 revolutions per minute for two hours and dried at 90 ℃ for six hours.
5) Adding deionized water, and separating most of graphite and the anode material by a suspension method.
6) The positive electrode material was dried and used for the next calcination experiment.
And 2, step: hydrogen-reducing positive electrode material
1) Weighing 2g of nickel-cobalt-manganese ternary material in a corundum crucible, and putting the corundum crucible into a tubular furnace.
2) Argon gas was introduced into the tube furnace and the temperature was raised to 300 ℃ at a rate of 5 ℃/min.
3) And when the tube furnace reaches the target temperature, closing the argon. Opening 5% of 2 And calcining the mixed gas/Ar at the flow rate of 150sccm for 135min, and observing the phase composition. And (3) characterizing the product by using an X-ray diffractometer technology, and verifying that the product is mainly a mixture of NiO and CoO. Because the positions of the diffraction peaks of CoO and NiO are similar, the diffraction peak is marked as NiO/CoO, an X-ray diffraction diagram is shown in figure 3, the horizontal axis marked 2 theta is a diffraction angle, and the measurement unit is degree.
4) After calcination at 300 ℃ for 135min, closing 5% 2 And (4) opening argon gas for purging and cooling the mixed gas/Ar.
And step 3: assembled electrolytic cell
1) The volume of the anode chamber of the cell was 10ml and the volume of the cathode chamber was 50ml. And slow filter paper is placed at the joint of each chamber and the communicating pipe to slow down the convection of the solution. About 60ml of Na is added 2 SO 4 And adding the electrolyte into an H-shaped electrolytic cell.
2) An electrode is inserted. Platinum wires (diameter 1 mm) were used for the anode, and platinum-plated titanium rods (diameter 6 mm) were used for the cathode.
3) And (3) putting about 0.1g of the reduced anode material into a small crucible, adding electrolyte into the small crucible, and after the material is settled and stabilized, putting the small crucible into the anode side of an H-shaped electrolytic cell, and adding the electrolyte. The temperature was raised to 90 ℃.
And 4, step 4: electrolytic water in H-shaped electrolytic cell
1) A voltage of 3.5V was applied between the anode and the cathode, and electrolysis was carried out for 24 hours. After the reaction, ni (OH) is generated in the cathode chamber 2 、Co(OH) 2 And Mn (OH) 2 The mixture was precipitated.
Comparative example 1:
the electrolysis experiment of the original cathode material without the reducing gas reaction did not include the step 2 hydrogen reduction, compared to example 1.
1) 0.1g of LiNi from example 1, step 1, was weighed 0.5 Co 0.2 Mn 0.3 O 2 And putting the anode material into a small crucible. Adding electrolyte into the crucible, after the material is settled and stabilized, putting the crucible into an anode chamber of an H-shaped electrolytic cell, adding the electrolyte, and heating to 90 ℃.
2) A voltage of 3.5V was applied between the cathode and the anode, and electrolysis was carried out for 24 hours.
And collecting the residual solid of the anode after reaction, and measuring the content of Li, ni, co and Mn elements in the residual solid by using an inductively coupled plasma emission spectrometer (ICP-OES). And calculating the leaching rates of Li, ni, co and Mn elements before and after the reaction. Leaching rate gamma M The calculation formula of (2) is as follows: gamma ray M ＝(c M ×m–c’ M ×m’)/(c M X m) in which c M And c' M Respectively the mass concentration of Li, ni, co or Mn in the anode chamber powder before and after leaching; m and m' are the mass of powder in the anode chamber before and after leaching, respectively. The leaching rate in other examples is calculated by using this formula.
Through calculation: example 1 by 5% 2 After 24-hour electrolysis experiment of the positive electrode material subjected to Ar reduction for 135min, the leaching rate of Li is 99%, the leaching rate of Ni is 97%, the leaching rate of Co is 82%, and the leaching rate of Mn is 42%.
Comparative example 1 the original positive electrode material, which was not subjected to the reaction of the reducing gas, had a leaching rate of Li of 95%, a leaching rate of Ni of 86%, a leaching rate of Co of 76%, and a leaching rate of Mn of 27% after 24-hour electrolysis experiment.
The above results indicate that H is not increased by 5% 2 H5% as compared with the original positive electrode material reduced with/Ar 2 The leaching rate of each metal element of the/Ar reduced anode material is obviously improved.
Example 2:
LiNi which is a positive electrode material of a waste lithium ion battery and is recycled by adopting a high-temperature hydrogen reduction and electrolytic water combined process 0.5 Co 0.2 Mn 0.3 O 2 The method comprises the following steps:
step 1: pretreating the waste lithium ion battery material
The same as in example 1.
Step 2: hydrogen-reducing cathode material
The same as in example 1.
And step 3: assembled electrolytic cell
The same as in example 1.
And 4, step 4: electrolytic water in H-shaped electrolytic cell
The same as in example 1. Except that in step 4 (1), the electrolysis time was 12 hours. After the reaction, ni (OH) is generated in the cathode chamber 2 、Co(OH) 2 And Mn (OH) 2 The mixture was precipitated.
Comparative example 2:
electrolytic experiment of original positive electrode material without reducing gas reaction
As in comparative example 1. Except that the electrolysis time of comparative example 2 was 12 hours.
And measuring the leaching rates of Li, ni, co and Mn after reaction by using an inductively coupled plasma emission spectrometer.
Through calculation: example 2 by 5% 2 After the anode material is subjected to Ar reduction for 135min, after 12-hour electrolysis experiment, the leaching rate of Li is 89%, the leaching rate of Ni is 61%, the leaching rate of Co is 49%, and the leaching rate of Mn is 29%.
The original positive electrode material of comparative example 2, which had not undergone the reducing gas reaction, had a leaching rate of Li of 78%, a leaching rate of Ni of 48%, a leaching rate of Co of 39%, and a leaching rate of Mn of 27% after the 12-hour electrolysis experiment.
The above results indicate that H is not increased by 5% 2 5% by weight of H, compared with the original positive electrode material of the/Ar reduction 2 The leaching rate of each metal element of the/Ar reduced anode material is obviously improved.
Example 3:
LiNi which is a waste lithium ion battery cathode material is recycled by adopting a high-temperature hydrogen reduction and electrolytic water combined process 0.5 Co 0.2 Mn 0.3 O 2 The method comprises the following steps:
step 1: pretreating the waste lithium ion battery material
The same as in example 1.
Step 2: hydrogen-reducing positive electrode material
The same as in example 1. Except that in step 2 (3), the hydrogen reduction time was increased to 180min. And (5) characterizing the product by using an X-ray diffractometer technology, and verifying that the product is mainly a mixture of NiO and CoO. The X-ray diffraction pattern is shown in fig. 4, with the horizontal axis labeled 2 θ as the diffraction angle and the metric in degrees.
And step 3: assembled electrolytic cell
The same as in example 1.
And 4, step 4: electrolytic water in H-shaped electrolytic cell
The same as in example 1. After the reaction, ni (OH) is generated in the cathode chamber 2 、Co(OH) 2 And Mn (OH) 2 The mixture was precipitated.
Comparative example 3: electrolytic experiment of original positive electrode material without reducing gas reaction
As in comparative example 1.
And measuring the leaching rates of Li, ni, co and Mn before and after the reaction by using an inductively coupled plasma emission spectrometer.
Through calculation: example 3 by 5% 2 After 24-hour electrolysis experiment, the leaching rate of Li is 100%, the leaching rate of Ni is 98%, the leaching rate of Co is 85% and the leaching rate of Mn is 54%.
Comparative example 3 the original positive electrode material, which was not subjected to the reaction of the reducing gas, had a leaching rate of Li of 95%, a leaching rate of Ni of 86%, a leaching rate of Co of 76%, and a leaching rate of Mn of 27% after the 24-hour electrolysis experiment.
The above results show that H is not 5% 2 5% by weight of H, compared with the original positive electrode material of the/Ar reduction 2 The leaching rate of each metal element of the/Ar reduced anode material is obviously improved.
Example 4:
LiNi which is a waste lithium ion battery cathode material is recycled by adopting a high-temperature hydrogen reduction and electrolytic water combined process 0.5 Co 0.2 Mn 0.3 O 2 The method comprises the following steps:
step 1: pretreating the waste lithium ion battery material
The same as in example 1.
And 2, step: hydrogen-reducing cathode material
The same as in example 1.
And 3, step 3: assembled electrolytic cell
The same as in example 1.
And 4, step 4: electrolyzed water in H-shaped electrolytic cell
The same as in example 1. Except that in step 4 (1), a voltage of 5V was applied between the anode and the cathode, and the electrolysis time was 24 hours. After the reaction, ni (OH) is generated in the cathode chamber 2 、Co(OH) 2 And Mn (OH) 2 The mixture was precipitated.
Comparative example 4: electrolytic experiment of original positive electrode material without reducing gas reaction
As in comparative example 1. Except that comparative example 4 was carried out for 24 hours by applying a voltage of 5V between the cathode and the anode.
And measuring the leaching rates of Li, ni, co and Mn before and after the reaction by using an inductively coupled plasma emission spectrometer.
Through calculation: example 4 by 5% 2 After 24 hours and 5V electrolysis experiments, the leaching rate of Li is 100%, the leaching rate of Ni is 100%, the leaching rate of Co is 99%, and the leaching rate of Mn is 70% of the anode material reduced by Ar for 135 min.
Comparative example 4 the original positive electrode material, which was not subjected to the reaction of the reducing gas, had a leaching rate of Li of 100%, a leaching rate of Ni of 100%, a leaching rate of Co of 96%, and a leaching rate of Mn of 45% after the 24-hour electrolysis experiment.
The above results show that H is not 5% 2 5% by weight of H, compared with the original positive electrode material of the/Ar reduction 2 The leaching rate of each metal element of the/Ar reduced anode material is obviously improved.
Example 5:
method for recycling positive electrode material LiMn in waste lithium ion battery by adopting high-temperature hydrogen reduction and electrolytic water combined process 2 O 4 The method comprises the following steps:
step 1: pretreating the waste lithium ion battery material
The same as in example 1. The difference lies in that the anode material of the selected waste lithium battery is LiMn 2 O 4 。
Step 2: hydrogen-reducing cathode material
1) Weighing 1.3g LiMn 2 O 4 The material is put into a corundum crucible and put into a tube furnace.
2) Argon is introduced into the tube furnace, and the temperature is raised to 850 ℃ at the speed of 5 ℃/min.
3) And when the tube furnace reaches the target temperature, closing the argon. Opening 5% of H 2 And (3) calcining the mixed gas/Ar at the flow rate of 150sccm for 150min, and observing the phase composition. The product is characterized by an X-ray diffractometer technology, and is verified to be mainly MnO. The X-ray diffraction pattern is shown in fig. 5, where the horizontal axis indicates the diffraction angle 2 θ and the unit of measurement is degree.
4) After calcination at 850 ℃ for 150min, 5% are turned off 2 And opening argon gas in the mixed gas of/Ar, and purging to reduce the temperature.
And step 3: assembled electrolytic cell
The same as in example 1. In addition, nylon filter cloth is sleeved on the anode electrode and used for collecting generated manganese dioxide.
And 4, step 4: electrolytic water in H-shaped electrolytic cell
The same as in example 1. After the reaction, mn (OH) is generated in the cathode chamber 2 And (4) precipitating.
Comparative example 5: electrolytic experiment of original positive electrode material without reducing gas reaction
The electrolysis experiment of the original cathode material without the reducing gas reaction did not include the step 2 hydrogen reduction, compared to example 5.
1) 0.1g of LiMn from example 5, step 1, was weighed out 2 O 4 And (4) putting the anode material into a small crucible. Adding electrolyte into the crucible, after the material is settled and stabilized, putting the crucible into an anode chamber of an H-shaped electrolytic cell, adding the electrolyte, and heating to 90 ℃.
2) A voltage of 3.5V was applied between the cathode and the anode, and electrolysis was carried out for 24 hours.
Calculated as follows: example 5 by 5% 2 the/Ar is reduced for 150min at 850 ℃, and after 24-hour electrolysis experiment, the leaching rate of Li is 100 percent, and the leaching rate of Mn is 98 percent.
Comparative example 5 the original positive electrode material, which was not subjected to the reaction of the reducing gas, had a leaching rate of Li of 100% and a leaching rate of Mn of 39% after 24 hours of the electrolysis experiment.
The above results show that H is not 5% 2 5% by weight of H, compared with the original positive electrode material of the/Ar reduction 2 The leaching rate of manganese metal elements of the positive electrode material after Ar reduction is greatly improved.
Example 6:
the LiCoO serving as the cathode material in the waste lithium ion battery is recycled by adopting a high-temperature hydrogen reduction and electrolytic water combined process 2 Method (2)The method comprises the following steps:
step 1: pretreating the waste lithium ion battery material
The same as in example 1. The difference is that the anode material of the selected waste lithium battery is LiCoO 2 。
And 2, step: hydrogen-reducing positive electrode material
1) Weighing 1g LiCoO 2 The material is put into a corundum crucible and put into a tube furnace.
2) Argon was introduced into the tube furnace and the temperature was raised to 375 ℃ at a rate of 5 ℃/min.
3) And when the tube furnace reaches the target temperature, closing the argon. Opening 5% of 2 And (3) calcining the mixed gas/Ar at the flow rate of 150sccm for 50min, and observing the phase composition. The product was characterized by X-ray diffractometer technology, verifying that the product was predominantly CoO phase. The X-ray diffraction pattern is shown in fig. 6, with the horizontal axis labeled 2 θ as the diffraction angle and the metric in degrees.
4) After calcination at 375 ℃ for 50min, 5% are closed 2 And opening argon gas in the mixed gas of/Ar, and purging to reduce the temperature.
And step 3: assembled electrolytic cell
The same as in example 1. The difference lies in that the anode material of the selected waste lithium battery is LiCoO 2 。
And 4, step 4: electrolyzed water in H-shaped electrolytic cell
1) A voltage of 3.5V was applied between the anode and the cathode, and electrolysis was carried out for 24 hours. After the reaction, co (OH) is formed at the cathode 2 And (4) precipitating.
Comparative example 6: electrolytic experiment of original positive electrode material without reducing gas reaction
The electrolysis experiment of the original cathode material, which did not react with the reducing gas, did not include the hydrogen reduction of step 2, as compared to example 6.
1) 0.1g of LiCoO from example 6, step 1, was weighed out 2 And putting the anode material into a small crucible. Adding electrolyte into the crucible, after the material is settled and stabilized, putting the crucible into an anode chamber of an H-shaped electrolytic cell, adding the electrolyte, and heating to 90 ℃.
2) A voltage of 3.5V was applied between the cathode and the anode, and electrolysis was carried out for 24 hours.
Through calculation: example 6 by 5% 2 the/Ar is reduced for 50min at 375 ℃, and after 24-hour electrolysis experiment, the leaching rate of Li is 100 percent, and the leaching rate of Co is 99 percent.
Comparative example 6 the original positive electrode material, which was not subjected to the reaction of the reducing gas, had a leaching rate of Li of 96% and a leaching rate of Co of 45% after 24 hours of the electrolysis experiment.
The above results indicate that H is not increased by 5% 2 H5% as compared with the original positive electrode material reduced with/Ar 2 The leaching rate of cobalt element of the positive electrode material after Ar reduction is greatly improved.
Example 7:
the LiCoO serving as the cathode material in the waste lithium ion battery is recycled by adopting a high-temperature hydrogen reduction and electrolytic water combined process 2 The method comprises the following steps:
step 1: pretreating the waste lithium ion battery material
The same as in example 6.
Step 2: hydrogen-reducing positive electrode material
The same as in example 6.
And step 3: assembled electrolytic cell
The same as in example 6. Except that the temperature of the solution was controlled to 40 ℃.
And 4, step 4: electrolytic water in H-shaped electrolytic cell
The same as in example 6. After the reaction, co (OH) is generated in the cathode chamber 2 And (4) precipitating.
Comparative example 7: electrolytic experiment of original positive electrode material without reducing gas reaction
As in comparative example 6. Except that the temperature during electrolysis was 40 ℃.
Through calculation: example 7 by 5% 2 and/Ar reduces the anode material for 50min at 375 ℃, and after 24-hour electrolysis experiment at 40 ℃, the leaching rate of Li is 99 percent and the leaching rate of Co is 89 percent.
Comparative example 7 the original positive electrode material, which had not been subjected to the reaction of the reducing gas, had a leaching rate of Li of 83% and a leaching rate of Co of 24% after 24 hours of the electrolytic experiment at 40 ℃.
The above results show that H is not 5% 2 5% by weight of H, compared with the original positive electrode material of the/Ar reduction 2 The leaching rate of cobalt element can still be greatly improved by the anode material subjected to Ar reduction at a lower electrolysis temperature.
Example 8:
MnO as main component for reducing positive electrode material in zinc-manganese battery by adopting high-temperature hydrogen 2 The method comprises the following steps:
1) 0.5g of MnO was weighed 2 The material is put into a corundum crucible and put into a tubular furnace.
2) 5% by volume in a tube furnace 2 The flow rate of the mixed gas/Ar is 150sccm. The temperature is raised to 850 ℃ at a speed of 5 ℃/min. Calcining for 150min, and cooling.
3) And characterizing the product by using an X-ray diffractometer technology, and verifying that the product after hydrogen reduction is MnO. The X-ray diffraction pattern is shown in fig. 7, with the horizontal axis labeled 2 θ as the diffraction angle and the metric in degrees.
The above results indicate that MnO, the main component of the positive electrode material in the zinc-manganese battery 2 MnO is generated after hydrogen reduction. MnO is readily soluble in acid. The method shows that the MnO which is the anode material in the waste zinc-manganese battery can be efficiently recovered by adopting the combined process of high-temperature hydrogen reduction and electrolytic water 2 。
Example 9
The LiCoO serving as the cathode material in the waste lithium ion battery is recycled by adopting a high-temperature hydrogen reduction and electrolytic water combined process 2 The method comprises the following steps:
step 1: pretreating the waste lithium ion battery material
The same as in example 6.
Step 2: hydrogen-reducing cathode material
The same as in example 6.
And 3, step 3: assembled electrolytic cell
The same as in example 6. Except that the temperature of the solution was controlled to 23 ℃.
And 4, step 4: electrolyzed water in H-shaped electrolytic cell
The same as in example 6. After the reaction, co (OH) is generated in the cathode chamber 2 And (4) precipitating.
Comparative example 9: electrolytic experiment of original positive electrode material without reducing gas reaction
As in comparative example 6. Except that the temperature during electrolysis was 23 ℃.
Calculated as follows: example 9% by 5 2 and/Ar reduces the anode material for 50min at 375 ℃, and after 24-hour electrolysis experiment at 23 ℃, the leaching rate of Li is 97 percent, and the leaching rate of Co is 78 percent.
Comparative example 9 the original positive electrode material, which had not been subjected to the reaction of the reducing gas, had a leaching rate of Li of 33% and a leaching rate of Co of 12% after 24 hours of the electrolytic experiment at 23 ℃.
The above results indicate that H is not increased by 5% 2 H5% as compared with the original positive electrode material reduced with/Ar 2 The leaching rate of cobalt element can be greatly improved even if water is electrolyzed at room temperature by the positive electrode material subjected to Ar reduction.
The method for recycling metal elements in the anode material of waste batteries, which is proposed by the present invention, has been described by way of preferred embodiments, and it is obvious to those skilled in the art that the technology of the present invention can be implemented by modifying or appropriately changing and combining the process methods described herein without departing from the content, spirit and scope of the present invention. It is expressly intended that all such similar substitutes and modifications which are obvious to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A method for recycling metal elements in a positive electrode material of a waste battery comprises the following steps:
1) Providing waste cathode materials; calcining the spent positive electrode material in a reducing gas to provide a reducing reaction product;
2) Providing an electrolytic water system comprising an anode and a cathode, the anode comprising an anolyte, the anolyte comprising water, the anolyte being electrolyzed to provide O 2 And H + Said cathode comprising a catholyte, said catholyte comprising water, said catholyte beingElectrolysis to provide H 2 And OH - (ii) a Said H 2 Recycled as reducing gas for use in step 1);
3) Reacting the reductive reaction product of step 1) with the H electrolyzed in the anolyte of step 2) + Reacting to provide transition metal element ions and/or alkali metal ions;
4) Diffusing the transition metal ions provided in the step 3) into the catholyte with OH in the step 2) - Reacting to provide a hydroxide precipitate of the transition metal element.
2. The method for recycling metal elements in the anode materials of the waste batteries according to claim 1, wherein in the step 1), the waste anode materials are selected from anode materials of lithium ion batteries or other batteries; the other battery is selected from a sodium ion battery and a zinc ion battery; preferably, the waste cathode material is selected from LiCoO 2 、LiNi x Co y Mn 1-x-y O 2 、LiNi x Co y Al 1-x-y O 2 、LiNiO 2 、LiMn 2 O 4 、NaCoO 2 、NaNi x Co y Mn 1-x-y O 2 、MnO 2 Wherein 0 < x < 1,0 < y < 1,0 < z < 1, x + y + z =1; preferably, x is selected from 0.2 to 0.95; y is selected from 0.01 to 0.3.
3. The method for recycling metal elements in the positive electrode materials of the waste batteries according to claim 1, wherein in the step 1), the reducing gas is selected from hydrogen or a mixed gas of hydrogen and inert gas; preferably, the molar ratio of the hydrogen gas to the inert gas is 2 to 8:92 to 98 percent; the inert gas is selected from argon and/or nitrogen.
4. The method for recycling the metal elements in the anode materials of the waste batteries as claimed in claim 1, wherein in the step 1), the reaction temperature is 300-900 ℃; the reaction time is 1 to 24 hours;
and/or the reductive reaction product is a metal compound; the metal compound is one or a mixture of more of LiOH, naOH, niO, coO and MnO.
5. The method for recycling metal elements in the anode material of the waste battery as claimed in claim 1, wherein in the step 2), the anode is made of platinum wires;
and/or, in the step 2), the cathode is made of a platinum wire or a platinum-plated titanium rod;
and/or, in step 2), the anolyte is selected from a sodium salt aqueous solution electrolyte; the sodium salt is selected from Na 2 SO 4 、NaNO 3 And NaClO 4 One or more of;
and/or, in step 2), the catholyte is selected from a sodium salt aqueous solution electrolyte; the sodium salt is selected from Na 2 SO 4 、NaNO 3 And NaClO 4 One or more combinations of;
and/or, in step 3), the transition metal ions are selected from Ni 2+ 、Co 2+ 、Mn 2+ One or more of;
and/or, in step 3), the alkali metal ion is selected from Li + 、Na + One or more combinations of;
and/or, in the step 4), the hydroxide of the transition metal element is selected from Ni (OH) 2 、Co(OH) 2 、Mn(OH) 2 One or more combinations of;
and/or the reaction temperature of the anolyte and/or the catholyte is 20-95 ℃;
and/or the electrolytic voltage of the anolyte and/or the catholyte is 3-5V;
and/or the electrolysis time of the anolyte and/or the catholyte is 6-24 h.
6. The method for recycling metallic elements in the anode materials of waste batteries according to any one of claims 1 or 5,characterized in that the step 4) also comprises adding a soluble carbonate solution into the catholyte so that the Li provided in the step 3) + Diffusing into the catholyte to react with the soluble carbonate solution to provide Li 2 CO 3 And (4) precipitating.
7. The method for recycling metal elements in the positive electrode material of waste batteries according to claim 6, wherein the hydroxide precipitate of the transition metal elements and Li are collected 2 CO 3 Precipitating and roasting to provide a regenerated cathode material; preferably, the calcination is carried out in the air; the roasting temperature is 850-900 ℃;
and/or, the soluble carbonate solution is selected from Na 2 CO 3 And (3) solution.
8. An electrolysis system comprising a reduction reaction apparatus (2) and an electrolysis apparatus (1); the reduction reaction device (2) comprises a reaction cavity (21); the electrolysis device (1) comprises an anode (12) and a cathode (13), wherein the anode (12) and the cathode (13) are respectively connected with a power supply (11); also comprises a gas communicating pipeline (3); the cathode (13) is communicated with the reaction cavity (21) through a gas communication pipeline (3).
9. The electrolysis system according to claim 8, wherein the anode (12) comprises an anode body (121) and an anodic electrolysis chamber (122); an anolyte is arranged in the anode electrolysis chamber (122); the bottom of the anode electrolysis chamber (122) is provided with a sample tube (18); the anode body (121) is in contact with the anolyte; the anode body (121) is connected with the positive electrode of a power supply (11); the cathode (13) comprises a cathode body (131) and a cathodic electrolysis chamber (132); a catholyte is disposed in the catholyte chamber (132); the cathode body (131) is in contact with the catholyte; the cathode body (131) is connected with the negative electrode of the power supply (11); the device also comprises a communication chamber (14) for communicating the anode electrolysis chamber (122) with the cathode electrolysis chamber (132), and two sides of the communication chamber (14) are respectively provided with a diaphragm (17).
10. The electrolysis system according to claim 9, further comprising an oxygen outlet (15) in communication with the anolyte chamber (122);
and/or further comprising a hydrogen gas outlet (16) in communication with the cathode electrolysis chamber (132); the hydrogen outlet (16) is communicated with the gas communication pipeline (3);
and/or, the anode body (121) comprises an anode material thereon, the anode material comprising a platinum wire;
and/or the cathode body (131) comprises a cathode material comprising platinum wire or platinized titanium rod;
and/or the membrane (17) is selected from filter paper.
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