CN103199230A - Process for reversely recycling and preparing lithium nickel manganese oxide by taking waste lithium battery as raw material - Google Patents
Process for reversely recycling and preparing lithium nickel manganese oxide by taking waste lithium battery as raw material Download PDFInfo
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- CN103199230A CN103199230A CN2013100895093A CN201310089509A CN103199230A CN 103199230 A CN103199230 A CN 103199230A CN 2013100895093 A CN2013100895093 A CN 2013100895093A CN 201310089509 A CN201310089509 A CN 201310089509A CN 103199230 A CN103199230 A CN 103199230A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- 239000002994 raw material Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000004064 recycling Methods 0.000 title abstract description 6
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title abstract 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 153
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 98
- 239000011572 manganese Substances 0.000 claims abstract description 67
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 66
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000010936 titanium Substances 0.000 claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 27
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 26
- 238000005516 engineering process Methods 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 17
- 230000010355 oscillation Effects 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 238000011067 equilibration Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000001632 sodium acetate Substances 0.000 claims description 7
- 235000017281 sodium acetate Nutrition 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000003350 kerosene Substances 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 8
- 238000000151 deposition Methods 0.000 abstract description 6
- 239000010926 waste battery Substances 0.000 abstract description 3
- BLYYANNQIHKJMU-UHFFFAOYSA-N manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Mn++].[Ni++] BLYYANNQIHKJMU-UHFFFAOYSA-N 0.000 abstract 5
- 238000007781 pre-processing Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 12
- 229910001437 manganese ion Inorganic materials 0.000 description 12
- 229910001453 nickel ion Inorganic materials 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation 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
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UGPIGYYLADCIFW-UHFFFAOYSA-N dioxido(dioxo)manganese;nickel(2+) Chemical compound [Ni+2].[O-][Mn]([O-])(=O)=O UGPIGYYLADCIFW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
Images
Classifications
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- 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
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a process for reversely recycling and preparing lithium nickel manganese oxide by taking waste lithium batteries as raw materials. The process is characterized by comprising the following steps of: (1) preprocessing a positive battery plate of a waste lithium battery to obtain anode power; (2) dissolving the anode power in inorganic acid, and eliminating impurities to obtain mixed acid liquor containing nickel and manganese; (3) adding a nickel source or a manganese source into the mixed solution; (4) adding an acetate complexing agent, and regulating the ratio of the acetate concentration to the total metal ion concentration; (5) putting the mixed solution into an electrolytic bath to be electrolyzed, and depositing nickel manganese oxide on a titanium plate; (6) stopping the conduction of a direct current, taking the titanium plate out, separating the nickel manganese oxide on the titanium plate, and drying the nickel manganese oxide to obtain nickel manganese oxide powder; (7) and uniformly mixing the nickel manganese oxide powder and a lithium source, and then calcining the mixture to obtain lithium nickel manganese oxide. According to the process, a regenerated product having the performance the same with the performance of the original product can be obtained by the waste battery through a reverse recycling process, so that the resource utilization can be realized.
Description
Technical field
The present invention relates to nickel LiMn2O4 preparation technology, relating in particular to a kind of is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell.
Background technology
Along with the continuous development of digital product industry, people increase day by day to the demand of battery.The nickel LiMn2O4 is a kind of important anode material of lithium battery, produces and uses increasingly extensively, and market demand is bigger.When lithium battery is flourish, can predict, in the near future, behind the battery end of life, can enter the stage of scrapping, can calculate that with the quantity of present lithium battery its learies also is huge on an equal basis.
The waste lithium cell positive electrode is nickel LiMn2O4 etc., can reclaim and be utilized, and makes metal powder, metal oxide, chemical industry salt etc.But best mode still reclaims the nickel LiMn2O4 by reverse recovery technology, is prepared into battery material, realizes recycling.
At present, reclaiming the technology of nickel lithium manganate battery material, generally is to add precipitation reagent nickel manganese precipitated metal is come out in the purification of metals liquid of battery material, is prepared into nickel manganese presoma through high-temperature calcination then, mixes the lithium source again and prepares the nickel LiMn2O4.The precipitation reagent that uses can be the solid precipitation reagent, as carbonate; Can be the liquid precipitation agent also, as ammoniacal liquor.But the cost that feeds intake if ammoniacal liquor is made precipitation reagent, can produce ammonia nitrogen waste water than higher, and neither environmental protection also increases cost for wastewater treatment.
Electrodeposition process is present a kind of method that reclaims metal simple-substance, and still, because the deposition potential of nickel, manganese element is separated out nickel oxide and manganese oxide separately easily at a distance of bigger during electro-deposition, the difficult codeposition that takes place obtains Ni, Mn oxide; And ratio and the total concentration of nickel, manganese ion concentration is bigger to the appearance structure influence of Ni, Mn oxide in the reaction system, and therefore best nickel, the manganese ion concentration of report explanation electric deposition nickel Mn oxide do not arranged at present.
Summary of the invention
It is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell that purpose of the present invention provides a kind of, and this technology can obtain the reconstituted product identical with the original product performance with waste battery by reverse recovery technology, realizes recycling.
The objective of the invention is to be achieved through the following technical solutions: a kind of is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, may further comprise the steps:
(1) battery anode slice of getting waste and old lithium ion battery carries out preliminary treatment acquisition positive powder;
(2) described positive powder is dissolved in the inorganic acid, removal of impurities obtains containing the mix acid liquor of nickel and manganese;
(3) add nickel source or manganese source in the described mixed solution, regulate that the molar concentration rate of nickel and manganese is in the mixed solution (0.5-2) ﹕ 1, the metal ion total concentration is 1-5mol/L;
(4) add the acetate complexing agent, the ratio of acetate concentration and metal ion total concentration is 1 ~ 2 ﹕ 1;
(5) mixed solution is placed electrolysis tank, be heated to 85 ~ 95 ℃, constant temperature 10 ~ 15min is negative electrode with the titanium sheet then, and graphite rod is anode, feeds the constant current direct current, and the control current density is at 100 ~ 500A/m
2, keep 2 ~ 5h, Ni, Mn oxide is deposited on the titanium sheet;
(6) stop to feed direct current, take out the titanium sheet, the Ni, Mn oxide on the separating titanium sheet, drying obtains the Ni, Mn oxide powder;
(7) Ni, Mn oxide powder and lithium source mix, and carry out calcination processing then, obtain the nickel LiMn2O4.
In the present invention, according to the influence to crystal nucleation speed and size of the concentration of current density, temperature and solution.Under other condition same cases, adopt high current density, can make crystal nucleation fast, nucleus is many, and size is big, and the oversize chemical property that is unfavorable for the nickel LiMn2O4 is so highest current density is no more than 500A/m
2Adopt low current density, nucleation is slow, and nucleus is few, and size is little, but can reduce production efficiency, so minimum current density is not less than 100A/m
2Under other condition same cases, adopt high temperature, can accelerate the system reaction speed, but the too high meeting of temperature makes the water solution system boiling or closely boil, make the reaction system instability, so maximum temperature is no more than 95 ℃; Adopt low temperature, can make stable reaction, be conducive to crystal and evenly grow, the structure unanimity, but temperature is crossed low meeting production efficiency, so minimum temperature is not less than 85 ℃.Under other condition same cases, adopt highly concentrated solution, can increase product output, but excessive concentration can make crystal growth surpass the substrate volume, reunites, and is unfavorable for the chemical property of nickel LiMn2O4, so the highest total concentration of metal ion is no more than 5mol/L; Adopt low concentration solution, can guarantee the crystal growth space, but concentration crosses and lowly can make output lower, the waste resource is so the highest total concentration of metal ion is not less than 1mol/L.
The preliminary treatment of step of the present invention (1) is that battery cell is disassembled, and takes out positive plate, again with the positive plate fragmentation, and pyrolysis, vibrosieve makes positive powder and other materials physical separation;
The nickel source of step of the present invention (2) is a kind of in nickel chloride, nickelous sulfate, the nickel nitrate, described manganese source is a kind of in manganese chloride, manganese sulfate, the manganese nitrate, described inorganic acid is a kind of in hydrochloric acid, nitric acid and the sulfuric acid, wherein preferably adopt nitric acid, the oxidizability of nitric acid is to dissolve for front end, also be for electro deposition oxidation nickel manganese, can have saved feed intake step and the cost of oxidant.
Step of the present invention (2) removal of impurities is to purify by the extraction mode only to contain the acid solution of nickel, two kinds of metallic elements of manganese.
As an embodiment of the invention, described extraction detailed process is: control acid solution pH is 2 ~ 3, and adding is 30% P by volume fraction
20
4With volume fraction be the extractant that 70% sulfonated kerosene constitutes, the volume ratio of extractant and acid solution is 2 ﹕ 1, equilibration time is 15 ~ 30min, uses the back extraction of 2mol/L inorganic acid again, equilibration time is 15 ~ 30min, obtains mix acid liquor nickeliferous, manganese.
The acetate complexing agent of step of the present invention (4) is sodium acetate or potassium acetate.
It is that Ni, Mn oxide breaks away from the titanium sheet that step of the present invention (6) adopts sonic oscillation, and duration of oscillation is preferably 10 ~ 15min.The described dry pressure-filteration drying that adopts, soon the Ni, Mn oxide suspension behind the sonic oscillation carries out press filtration, and filter residue is placed heating furnace, is heated to 100 ℃, dry 30min.
The mass ratio in the described Ni, Mn oxide of step of the present invention (7) and lithium source is 3 ~ 5:1.The program of described calcination processing is for to be warming up to 200 ℃ with 2 ℃/min speed, and constant temperature 4h is warming up to 500 ~ 600 ℃, constant temperature 10 ~ 12h again.
Described step (7) lithium source is lithium carbonate or lithium hydroxide.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention is by the earlier synthetic Ni, Mn oxide of old and useless battery positive electrode, and synthetic new nickel manganate cathode material for lithium can obtain the reconstituted product identical with the original product performance with waste battery by reverse recovery technology again, realizes recycling.
(2) in the step of the synthetic Ni, Mn oxide of the present invention, can control speed and the size of crystal growth by the concentration of control current density, temperature and solution, be conducive to regulate and control character and the performance of synthetic material.
(3) the present invention comes out Ni, Mn oxide electrodeposition from solution, compare with traditional precipitation method, has saved the link of adding solid precipitation reagent or ammoniacal liquor, has saved the cost of auxiliary material, and process do not produce ammonia nitrogen waste water and pollute, and has reduced cost for wastewater treatment.
(4) the present invention controls ratio and the total concentration of nickel ion and manganese ion in the reaction system, and the Ni, Mn oxide that pattern is the homogeneous sphere, the synthesizing formula that provides a kind of prior art not have are provided in electro-deposition.
(5) the present invention uses acetate to be complexing agent, utilize acetate can with the character of nickel, manganese ion complexing, the deposition potential of the nickel that furthers, manganese element makes nickel, manganese element be easy to take place codeposition, solve nickel, manganese element because of the deposition potential apart from each other, separately the problem of deposition.
Description of drawings
Fig. 1 is the SEM figure of the embodiment of the invention one gained Ni, Mn oxide.
Fig. 2 is the SEM figure of contrast experiment's one gained Ni, Mn oxide.
Fig. 3 is the SEM figure of contrast experiment's two gained Ni, Mn oxides.
Embodiment
Embodiment one:
(1) battery cell is disassembled, taken out positive plate; Positive plate is pulverized, and pyrolysis adopts 60 purpose standard screens to sieve under vibration, obtains anodal powder 1846g.
(2) anodal powder is dissolved in the 10L nitric acid, insoluble matter removes by filter, and control filtrate pH is 2, adds the 20L extractant, and the component of extractant is that volume fraction is 30% P
20
4With volume fraction be 70% sulfonated kerosene, equilibration time is 15min, strips with 10L 2mol/L nitric acid again, equilibration time is 15min, obtain the mixed solution that solution is nickel nitrate and manganese nitrate, record that nickel ion concentration is 0.60mol/L in the solution, manganese ion concentration is 0.63mol/L.
(3) in the mixed solution of step (2), add the 54.84g nickel nitrate, making nickel ion and manganese ion concentration ratio is 1 ﹕ 1.
(4) add the 1033.2g sodium acetate, the ratio of acetate concentration and metal ion total concentration is 1 ﹕ 1.
(5) pour above-mentioned solution into electrolysis tank, be heated to 85 ℃, constant temperature 10min.Inserting titanium sheet and graphite rod, is negative electrode with the titanium sheet, is anode with the graphite rod, is communicated with galvanostat, feeds the constant current direct current, and the control current density is 100A/m
2, keep 2h, Ni, Mn oxide is deposited on the titanium sheet;
(6) stop to feed direct current, take out the titanium sheet, place water, sonic oscillation 5min, Ni, Mn oxide breaks away from the titanium sheet, and the Ni, Mn oxide suspension behind the sonic oscillation is carried out press filtration, and filter residue is placed heating furnace, be heated to 100 ℃, dry 30min obtains Ni, Mn oxide powder 942.22g;
(7) add the 242.75g lithium carbonate toward the Ni, Mn oxide powder, mix, place calciner, be warming up to 200 ℃ with 2 ℃/min speed, constant temperature 4h is warming up to 500 ℃ again, and constant temperature 10h obtains 1120.32g nickel LiMn2O4.The microstructure of Ni, Mn oxide as shown in Figure 1, this Ni, Mn oxide is spherical in shape, the structure unanimity, particle diameter is even.
Embodiment two:
(1) battery cell is disassembled, taken out positive plate; Positive plate is pulverized, and pyrolysis adopts 60 purpose standard screens to sieve under vibration, obtains anodal powder 1950g.
(2) anodal powder is dissolved in the 10L hydrochloric acid, insoluble matter removes by filter, control filtrate pH is 2, adds the 20L extractant, and the component of extractant is that volume fraction is that 30% P204 and volume fraction are 70% sulfonated kerosene, equilibration time is 20min, strip with 10L 2mol/L hydrochloric acid, equilibration time is 20min, obtains the mixed solution that solution is nickel chloride and manganese chloride again, record that nickel ion concentration is 1.25mol/L in the solution, manganese ion concentration is 2.2mol/L.
(3) in the mixed solution of step (2), add the 390g manganese chloride, making nickel ion and manganese ion concentration ratio is 0.5 ﹕ 1.
(4) add the 3075g sodium acetate, the ratio of acetate concentration and metal ion total concentration is 1 ﹕ 1.
(5) pour above-mentioned solution into electrolysis tank, be heated to 90 ℃, constant temperature 10min.Inserting titanium sheet and graphite rod, is negative electrode with the titanium sheet, is anode with the graphite rod, is communicated with galvanostat, feeds the constant current direct current, and the control current density is 200A/m
2, keep 3h, Ni, Mn oxide is deposited on the titanium sheet.
(6) stop to feed direct current, take out the titanium sheet, place water, sonic oscillation 5min, Ni, Mn oxide breaks away from the titanium sheet, and the Ni, Mn oxide suspension behind the sonic oscillation is carried out press filtration, and filter residue is placed heating furnace, be heated to 100 ℃, dry 30min obtains Ni, Mn oxide powder 3412.5g.
(7) add the 1387.5g lithium carbonate toward the Ni, Mn oxide powder, mix, place calciner, be warming up to 200 ℃ with 2 ℃/min speed, constant temperature 4h is warming up to 500 ℃ again, and constant temperature 10h obtains 3675g nickel LiMn2O4.
Embodiment three:
(1) battery cell is disassembled, taken out positive plate; Positive plate is pulverized, and pyrolysis adopts 60 purpose standard screens to sieve under vibration, obtains anodal powder 1872g.
(2) anodal powder is dissolved in the 10L sulfuric acid, insoluble matter removes by filter, control filtrate pH is 3, adds the 20L extractant, and the component of extractant is that volume fraction is that 30% P204 and volume fraction are 70% sulfonated kerosene, equilibration time is 30min, strip with 10L 2mol/L sulfuric acid, equilibration time is 30min, obtains the mixed solution that solution is nickelous sulfate and manganese sulfate again, record that nickel ion concentration is 1.2mol/L in the solution, manganese ion concentration is 1mol/L.
(3) in the mixed solution of step (2), add the 1240g nickelous sulfate, making nickel ion and manganese ion concentration ratio is 2 ﹕ 1.
(4) add the 2940g sodium acetate, the ratio of acetate concentration and metal ion total concentration is 1 ﹕ 1.
(5) pour above-mentioned solution into electrolysis tank, be heated to 95 ℃, constant temperature 10min.Inserting titanium sheet and graphite rod, is negative electrode with the titanium sheet, is anode with the graphite rod, is communicated with galvanostat, feeds the constant current direct current, and the control current density is 500A/m
2, keep 5h, Ni, Mn oxide is deposited on the titanium sheet.
(6) stop to feed direct current, take out the titanium sheet, place water, sonic oscillation 5min, Ni, Mn oxide breaks away from the titanium sheet, and the Ni, Mn oxide suspension behind the sonic oscillation is carried out press filtration, and filter residue is placed heating furnace, be heated to 100 ℃, dry 30min obtains Ni, Mn oxide powder 2730g;
(7) add the 1110g lithium carbonate toward the Ni, Mn oxide powder, mix, place calciner, be warming up to 200 ℃ with 2 ℃/min speed, constant temperature 4h is warming up to 500 ℃ again, and constant temperature 10h obtains 2940g nickel LiMn2O4.
The contrast experiment one:
Formulation components is 0.63mol/L for nickel nitrate concentration, and manganese nitrate concentration is 0.21mol/L, and sodium acetate concentration is the solution 10L of 0.84mol/L, and nickel ion is 3 ﹕ 1 with the manganese ion concentration ratio; Pour above-mentioned solution into electrolysis tank, be heated to 85 ℃, constant temperature 10min; Inserting titanium sheet and graphite rod, is negative electrode with the titanium sheet, is anode with the graphite rod, is communicated with galvanostat, feeds the constant current direct current, and the control current density is 100A/m
2, keep 2h, Ni, Mn oxide is deposited on the titanium sheet; Stop to feed direct current, take out the titanium sheet, place water, sonic oscillation 5min, Ni, Mn oxide breaks away from the titanium sheet, and the Ni, Mn oxide suspension behind the sonic oscillation is carried out press filtration, and filter residue is placed heating furnace, be heated to 100 ℃, dry 30min obtains the Ni, Mn oxide powder.The microstructure of Ni, Mn oxide as shown in Figure 2, the not moulding of this Ni, Mn oxide, shape differs, no fixed dimension.
The contrast experiment two:
Formulation components is 0.21mol/L for nickel nitrate concentration, and manganese nitrate concentration is 0.63mol/L, and sodium acetate concentration is the solution 10L of 0.84mol/L, and nickel ion is 1 ﹕ 3 with the manganese ion concentration ratio; Pour above-mentioned solution into electrolysis tank, be heated to 85 ℃, constant temperature 10min; Inserting titanium sheet and graphite rod, is negative electrode with the titanium sheet, is anode with the graphite rod, is communicated with galvanostat, feeds the constant current direct current, and the control current density is 100A/m
2, keep 2h, Ni, Mn oxide is deposited on the titanium sheet; Stop to feed direct current, take out the titanium sheet, place water, sonic oscillation 5min, Ni, Mn oxide breaks away from the titanium sheet, and the Ni, Mn oxide suspension behind the sonic oscillation is carried out press filtration, and filter residue is placed heating furnace, be heated to 100 ℃, dry 30min obtains the Ni, Mn oxide powder.The microstructure of Ni, Mn oxide as shown in Figure 3, this Ni, Mn oxide is irregular sphere, reunites no fixed dimension mutually.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention rather than restriction, therefore every foundation essence technology of the present invention all belongs in the scope of technical solution of the present invention any trickle modification, equivalent variations and modification that above embodiment does.
Claims (10)
1. one kind is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that, may further comprise the steps:
(1) battery anode slice of getting waste and old lithium ion battery carries out preliminary treatment acquisition positive powder;
(2) described positive powder is dissolved in the inorganic acid, removal of impurities obtains containing the mix acid liquor of nickel and manganese;
(3) add nickel source or manganese source in described mixed solution, the molar concentration rate of nickel and manganese is 0.5 ~ 2 ﹕ 1 in the adjusting mixed solution, and the metal ion total concentration is 1 ~ 5mol/L;
(4) add the acetate complexing agent, the ratio of acetate concentration and metal ion total concentration is 1 ~ 2 ﹕ 1;
(5) mixed solution is placed electrolysis tank, be heated to 85 ~ 95 ℃, constant temperature 10 ~ 15min is negative electrode with the titanium sheet then, and graphite rod is anode, feeds the constant current direct current, and the control current density is at 100 ~ 500A/m
2, keep 2 ~ 5h, Ni, Mn oxide is deposited on the titanium sheet;
(6) stop to feed direct current, take out the titanium sheet, the Ni, Mn oxide on the separating titanium sheet, drying obtains the Ni, Mn oxide powder;
(7) Ni, Mn oxide powder and lithium source mix, and carry out calcination processing then, obtain the nickel LiMn2O4.
2. according to claim 1 is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that, the preliminary treatment of described step (1) is that battery cell is disassembled, take out positive plate, again with the positive plate fragmentation, pyrolysis, vibrosieve makes positive powder and other materials physical separation.
3. according to claim 1 is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that, the nickel source of described step (2) is a kind of in nickel chloride, nickelous sulfate and the nickel nitrate, described manganese source is a kind of in manganese chloride, manganese sulfate and the manganese nitrate, and described inorganic acid is a kind of in hydrochloric acid, nitric acid and the sulfuric acid.
4. according to claim 1 is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that, described step (2) removal of impurities is to adopt the extraction mode to purify only to contain the acid solution of nickel, two kinds of metallic elements of manganese.
5. according to claim 4 is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that, described extraction detailed process is: control acid solution pH is 2 ~ 3, and adding is 30% P by volume fraction
20
4With volume fraction be the extractant that 70% sulfonated kerosene constitutes, the volume ratio of extractant and acid solution is 2 ﹕ 1, equilibration time is 15 ~ 30min, uses the back extraction of 2mol/L inorganic acid again, equilibration time is 15 ~ 30min, obtains mix acid liquor nickeliferous, manganese.
6. according to claim 1 is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that, the acetate complexing agent of described step (4) is sodium acetate or potassium acetate.
7. according to claim 1 is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that, it is that Ni, Mn oxide breaks away from the titanium sheet that described step (6) adopts sonic oscillation, and duration of oscillation is preferably 10 ~ 15min; The described dry pressure-filteration drying that adopts.
8. according to claim 7 is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that described pressure-filteration drying places heating furnace for the Ni, Mn oxide suspension behind the sonic oscillation is carried out press filtration with filter residue, be heated to 100 ℃, dry 30min.
9. according to claim 1 is the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that, the mass ratio in the described Ni, Mn oxide of described step (7) and lithium source is 3 ~ 5:1, the program of described calcination processing is for to be warming up to 200 ℃ with 2 ℃/min speed, constant temperature 4h, be warming up to 500 ~ 600 ℃ again, constant temperature 10 ~ 12h.
According to claim 1 or 9 described be the technology that the reverse recovery of raw material prepares the nickel LiMn2O4 with the waste lithium cell, it is characterized in that described step (7) lithium source is lithium carbonate or lithium hydroxide.
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