CN105800586A - Method for purifying acid production tail gas and recycling nickel, cobalt, manganese and lithium by using waste lithium nickel cobalt manganese oxide - Google Patents
Method for purifying acid production tail gas and recycling nickel, cobalt, manganese and lithium by using waste lithium nickel cobalt manganese oxide Download PDFInfo
- Publication number
- CN105800586A CN105800586A CN201610315807.3A CN201610315807A CN105800586A CN 105800586 A CN105800586 A CN 105800586A CN 201610315807 A CN201610315807 A CN 201610315807A CN 105800586 A CN105800586 A CN 105800586A
- Authority
- CN
- China
- Prior art keywords
- positive plate
- lithium manganate
- absorption plant
- gas
- tail gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 108
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000011572 manganese Substances 0.000 title claims abstract description 76
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 29
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 12
- 239000002699 waste material Substances 0.000 title abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000002253 acid Substances 0.000 title abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 4
- 239000010941 cobalt Substances 0.000 title abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 title abstract 5
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 title abstract 5
- 238000004064 recycling Methods 0.000 title abstract 2
- 238000010521 absorption reaction Methods 0.000 claims abstract description 190
- 238000001914 filtration Methods 0.000 claims abstract description 144
- 238000000498 ball milling Methods 0.000 claims abstract description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims abstract description 86
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 53
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 53
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 53
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 48
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000010406 cathode material Substances 0.000 claims abstract description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 24
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 6
- 238000005056 compaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 119
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 82
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 80
- 239000000919 ceramic Substances 0.000 claims description 71
- 230000008569 process Effects 0.000 claims description 65
- 239000003159 antacid agent Substances 0.000 claims description 62
- 239000003054 catalyst Substances 0.000 claims description 58
- 239000007774 positive electrode material Substances 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 53
- 229940069428 antacid Drugs 0.000 claims description 44
- 230000001458 anti-acid effect Effects 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 43
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 229910052720 vanadium Inorganic materials 0.000 claims description 40
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 40
- 238000011049 filling Methods 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 37
- 239000013078 crystal Substances 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 36
- 239000013589 supplement Substances 0.000 claims description 36
- 238000009413 insulation Methods 0.000 claims description 33
- 239000003595 mist Substances 0.000 claims description 27
- 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 claims description 22
- 239000004744 fabric Substances 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 19
- 239000005030 aluminium foil Substances 0.000 claims description 18
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 18
- 238000010792 warming Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 16
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 9
- 238000012544 monitoring process Methods 0.000 claims description 6
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000000706 filtrate Substances 0.000 abstract description 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 166
- 241000196324 Embryophyta Species 0.000 description 101
- 238000001035 drying Methods 0.000 description 16
- 229910052738 indium Inorganic materials 0.000 description 15
- 239000011656 manganese carbonate Substances 0.000 description 15
- 235000006748 manganese carbonate Nutrition 0.000 description 15
- 229940093474 manganese carbonate Drugs 0.000 description 15
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 239000001117 sulphuric acid Substances 0.000 description 12
- 235000011149 sulphuric acid Nutrition 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- 238000013459 approach Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- QJFSQWZVVOVYEZ-UHFFFAOYSA-N [Li+].[Li+].[Co++].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Li+].[Co++].[O-][Mn]([O-])(=O)=O.[O-][Mn]([O-])(=O)=O QJFSQWZVVOVYEZ-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910011396 LiCoxNiyMnzO2 Inorganic materials 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- DDXROPFGVVLFNZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) tricarbonate Chemical compound [Mn+2].[Co+2].C([O-])([O-])=O.[Ni+2].C([O-])([O-])=O.C([O-])([O-])=O DDXROPFGVVLFNZ-UHFFFAOYSA-H 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- -1 antacid sulfur dioxide Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NSQOWYPJQKUQEJ-UHFFFAOYSA-N N.S(=O)([O-])[O-].[NH4+].[NH4+] Chemical compound N.S(=O)([O-])[O-].[NH4+].[NH4+] NSQOWYPJQKUQEJ-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- OXSWKJLAKXNIFG-UHFFFAOYSA-N azane sulfuric acid Chemical compound N.N.N.OS(O)(=O)=O OXSWKJLAKXNIFG-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 238000003835 carbonate co-precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000007979 citrate buffer Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- SJZFFCZQDPVHQI-UHFFFAOYSA-N potassium;sulfurous acid Chemical compound [K].OS(O)=O SJZFFCZQDPVHQI-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
Abstract
The invention discloses a method for purifying acid production tail gas and recycling nickel, cobalt, manganese and lithium by using waste lithium nickel cobalt manganese oxide. The method comprises the following steps: discharging and disassembling a waste lithium ion battery to obtain a waste positive plate; performing roasting and water dissolution of the waste positive plate and filtering to obtain waste lithium nickel cobalt manganese oxide; mixing the waste lithium nickel cobalt manganese oxide with sodium sulfate and performing ball milling; putting the ball milling product into an absorption device; converting the acid production tail gas and introducing into the absorption device; discharging the gas meeting the discharge standard from the absorption device to the atmosphere; taking out the mixture in the absorption device and leaching with water; adding a sodium carbonate solution into the solution and filtering; adding lithium carbonate into the filter residue; performing ball milling, compaction and roasting to obtain a lithium nickel cobalt manganese oxide cathode material with good electrochemical performance again; and crystallizing the filtrate to obtain sodium sulfate.
Description
Technical field
The present invention relates to the use of useless nickle cobalt lithium manganate purify antacid tail gas and reclaim the technology of nickel cobalt manganese lithium.
Background technology
Sulphuric acid is widely used in chemical fertilizer industry, metallurgical industry, petroleum industry, mechanical industry, medical industry, the production of detergent, war industry, atomic energy industry and aerospace industry etc..But sulfuric acid industry is also the chemical industry of high pollution, containing sulfur dioxide, sulfuric acid mist in the tail gas produced in sulphuric acid process.The antacid tail gas of sulfuric acid industry every year to gas pollutants such as the substantial amounts of sulfur dioxide of airborne release, severe contamination environment.China has issued " sulfuric acid industry pollutant emission standard " (GB26132-2010) on 30th in December in 2010, the discharge of antacid tail gas is clearly required, it may be assumed that after 2013, the content of the antacid sulfur dioxide in tail gas of all newly-built and existing sulphuric acid production enterprises discharge have to be lower than 400mg/m3, sulfuric acid mist have to be lower than 30mg/m3.And current sulfuric acid industry SO in the tail gas that double-absorption production procedure is discharged2Content be typically in 600 ~ 1400mg/m3Left and right, it is impossible to directly to airborne release.
Antacid tail gas to pass through and removes sulfuric acid mist and make SO2Content reach could emptying after standard.The disclosed method reporting for work antacid treating tail gas has: sodium carbonate absorption process, sodium hydroxide absorption process, lime absorption, magnesium oxide absorption process, ammonia absorption process, ammonia ammonium sulphate process, ammonia-ammonium sulfite, ammonia-ammonium hydrogen sulfate method, sulfurous acid-Potassium acid sulfite method, peroxy-disulfuric acid conversion method, basic aluminum sulfate solution absorption method, Citrate Buffer, Exchange Resin by Adsorption, activated carbon adsorption conversion method etc..Wherein, sodium carbonate absorption process is to SO in antacid tail gas2Absorbance higher and obtain sodium sulfite product, but sodium sulfite market is limited, and also needs to be continuously added antioxidant in absorption process and stop sodium sulfite to be oxidized to sodium sulfate, and when the price of sodium carbonate is higher than sodium sulfite, this method is just uneconomical.Calx absorption process adopts lime water or lime cream washing antacid tail gas, the method technology maturation, and production cost is low, but SO2Absorption rate is slow, absorbability is little, the CaSO of generation3And CaSO4Easily blocking pipeline and equipment, this method produces substantial amounts of waste residue in addition, and these waste residues cause serious secondary pollution to environment.Ammonia absorption process adopts liquefied ammonia or ammonia as absorbent, and absorption efficiency is high, desulfurization is thorough, but ammonia is volatile, and the consumption of absorbent is big, and additionally the source of ammonia is limited by regions bigger.Sodium hydroxide absorption process is to use sodium hydroxide to administer antacid tail gas, SO2Absorbability is big, absorption rate is fast, efficiency is high, but maximum problem is that feed hydrogen sodium oxide is more expensive, and the cost of antacid treating tail gas is high.Additionally, the problem of other antacid method for treating tail gas several general character of all ubiquities: 1) raw materials used price height, investment is relatively big, and Operation and Maintenance is relatively costly；2) the side-product added value obtained after antacid treating tail gas is low.
Lithium ion battery is the secondary cell of new generation developed rapidly the nineties in 20th century, is widely used in small-sized portable electronic communication product and electric vehicle.Nickel-cobalt lithium manganate cathode material is due to the advantage such as have electrochemistry capacitance height, good cycle, synthesis is easy, cost is low, safety is good, instead of cobalt acid lithium in recent years gradually, be widely used at compact lithium cell positive electrode and lithium-ion-power cell field.Owing to the service life of lithium ion battery is generally 2-3, therefore, scrap lithium ion battery is brought environmental pollution and resource reutilization problem are increasingly subject to pay attention to.
The method from useless nickle cobalt lithium manganate recovery valuable metal reported at present has, and patent [CN201310736549] reports a kind of with the addition of Na2SO3The sulfuric acid solution method of dissolving useless nickel-cobalt lithium manganate material.Patent [CN201310736528] reports the method that the mixed solution of a kind of nitric acid and sulphuric acid dissolves useless nickel-cobalt lithium manganate material.Patent [CN201310736522] reports the method that the mixed solution of a kind of nitric acid and sulphuric acid dissolves useless nickle cobalt lithium manganate lithium ion battery plus-negative plate material and pasture powder.Patent [CN201310736539] reports the method that the mixed solution of a kind of nitric acid and sulphuric acid dissolves useless nickle cobalt lithium manganate lithium ion battery plus-negative plate composite material and corn stalk powder.Patent [CN201310736623] reports the method that the mixed solution of a kind of nitric acid and sulphuric acid dissolves useless nickle cobalt lithium manganate lithium ion battery plus-negative plate composite material and levigate pyrolusite.Patent [CN201310736485] reports the method that the mixed solution of a kind of nitric acid and sulphuric acid dissolves useless nickle cobalt lithium manganate lithium ion battery plus-negative plate composite material and the high concentrated organic wastewater without benzene ring substance.Patent [CN201310736513] reports the method that the mixed solution of a kind of nitric acid and sulphuric acid dissolves useless nickle cobalt lithium manganate lithium ion battery plus-negative plate composite material and grassiness powder.Patent [CN201310630608] discloses a kind of method preparing nickel-cobalt lithium manganate cathode material for raw material with waste and old lithium ion battery, adopting organic acid citric acid is leaching agent and gel, prepares nickel-cobalt lithium manganate cathode material by collosol and gel-hydrothermal reaction coupling method.Patent [CN201310123337] reports a kind of method of waste and old ter-polymers dynamic lithium battery resource, waste and old ter-polymers dynamic lithium battery carries out discharging, disassembling, and the immersion of battery pole piece NaOH solution, acetic acid immersion, acetone soak, filtering drying obtain nickle cobalt lithium manganate tertiary cathode material and carbon negative pole material.Patent [CN201210421198] discloses a kind of method being prepared nickle cobalt lithium manganate by waste and old electrokinetic cell, the positive plate of old and useless battery pulverized, sieve, acid-soluble solution, nickel salt, cobalt salt, manganese salt and ammonia is added in filtrate, filter, dry, obtain nickel cobalt manganese hydroxide powder, in nickel cobalt manganese hydroxide powder, add lithium carbonate, after calcining, obtain nickle cobalt lithium manganate.Patent [CN201210230857] reports a kind of waste lithium ion cell anode material full constituent resource recycle method, adopt the active substance in fluorine-containing aqueous solutions of organic acids separating waste, worn anode material for lithium-ion batteries and aluminum paper tinsel, high-temperature roasting is carried out respectively containing lithium active substance, alkali liquor remove impurity processes, nickel cobalt manganese carbonate ternary precursor is prepared in leachate ammonium carbonate co-precipitation, active substance and nickel cobalt manganese carbonate ternary precursor component of mixture after process regulate and control, after allocating a certain proportion of lithium carbonate into, high temperature solid-phase sintering prepares nickle cobalt lithium manganate ternary composite cathode material again.Patent [CN201110243034] provides a kind of waste and old electrokinetic cell ternary system anode material processing method, comprises the steps: alkali leaching, Ore Leaching nickel lithium and manganese cobalt, separates nickel lithium and manganese cobalt, reclaims nickel, reclaims lithium, Call Provision, recovery manganese.Patent [CN201010209830] reports a kind of method of Call Provision, nickel and manganese from waste lithium cell, the positive pole black powder that will obtain in useless ion battery, first adopts dilute sulfuric acid to carry out low acid-soluble solution, then adopts Na2SO5Or Na2SO3Or Fe powder adds concentrated sulphuric acid and carries out reduction of dissolved, high-concentration sulfuric acid is finally adopted to carry out acid-soluble solution.Patent [CN200910059700] describes the leaching method of a kind of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery, is added in nitric acid by isolated anode and cathode mixed materials from waste LiCoxNiyMnzO 2 battery and passes into industry pure oxygen and carries out the leaching of anode and cathode mixed materials of waste LiCoxNiyMnzO 2 battery.Patent [CN200810198972] discloses a kind of method preparing nickle cobalt lithium manganate for raw material with waste and old lithium ion battery.Sulphuric acid and hydrogen peroxide system is adopted to leach the positive electrode obtained in used Li ion cell, pH value is regulated then through nickel, cobalt, the adjustment of manganese element mol ratio, ammonium carbonate in abstraction impurity removal, solution, the nickel cobalt manganese carbonate precursor obtained allocates appropriate lithium carbonate into, the nickle cobalt lithium manganate battery material that high temperature sintering synthesis is active.
It has been reported that the method reclaiming valuable metal from useless nickle cobalt lithium manganate, recovery technology still has to use related chemistry reagent in a large number, such as sulphuric acid, hydrogen peroxide, sodium thiosulfate, hydrochloric acid, nitric acid, sodium bisulfate, sodium pyrosulfate etc., this makes the technology cost recovery currently reclaiming valuable metal from useless nickle cobalt lithium manganate be difficult to reduce.
Summary of the invention
It is an object of the invention to provide and a kind of utilize useless nickle cobalt lithium manganate to purify antacid tail gas the method that reclaims nickel cobalt manganese lithium.
The present invention utilizes useless nickle cobalt lithium manganate to purify antacid tail gas the method reclaiming nickel cobalt manganese lithium, the steps include:
Step (1): collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 1-3h in sodium hydrate aqueous solution；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Collect and make, with nickle cobalt lithium manganate, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；The positive plate obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5-1h from room temperature, then naturally cool to room temperature；Taking out through the positive plate of roasting, put into by positive plate equipped with filling in the container of water and stirring 5-30min, sieved by the mixture screen cloth in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and makes furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；
Step (2): mixed with sodium sulfate by useless nickle cobalt lithium manganate, then ball milling in ball mill, load the mixture after ball milling in absorption plant；Mixture after loading ball milling in the identical absorption plant of another one uses in step (3) as standby absorption plant；In this step, the source of sodium sulfate is the sodium sulfate or the two mixture being mixed to form with arbitrary proportion that obtain in the sodium sulfate chemical products or step (5) bought；
Step (3): from gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into equipped with the conversion system of vanadium catalyst carries out conversion operation again, the condition of conversion operation is: gasinlet temperature 400-405 DEG C, flow velocity 0.23-1.2m/s, in conversion system, the filling of vanadium catalyst is rated for: 0.3-0.6m3Catalyst/(1000m3Antacid tail gas h)；From conversion system gas out pass into described in step (2) have been charged into ball milling after mixture absorption plant carry out absorption operation, the condition of absorption operation is: temperature 300-450 DEG C, inlet gas flow velocity 0.2-1.2m/s；SO in monitoring absorption plant exit gas2Content whether lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, as reached requirement, discharge to air after the gas cooling that absorption plant is exported；As monitored SO in absorption plant exit gas2Content reach 400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then no longer pass into from conversion system gas out in this absorption plant, by passing into from conversion system gas out, the standby absorption plant described in step (2) carry out the absorption operation under the same terms and SO in exit gas simultaneously2Content, sulfuric acid mist the monitoring of content；Taking out the mixture in the absorption plant no longer passing into conversion system exit gas in this step, the mixture that this absorption plant then returns to after being again loaded into ball milling in step (2) uses in this step as standby absorption plant；
Step (4): being leached with the water of 20-50 DEG C when stirring by the mixture in the absorption plant no longer passing into conversion system exit gas in step (3), extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate being warmed up to 95-98 DEG C, sodium carbonate liquor is slowly added to leachate, then filter, washing filtering residue also dries, and analyzes the content of Ni, Co, Mn in filtering residue, then supplements nickelous carbonate (NiCO toward filtering residue3), cobalt carbonate (CoCO3), manganese carbonate (MnCO3) in one or both, make the Ni in filtering residue after supplementing, Co, Mn mol ratio meets the requirement of 1:1:1, analyze Li in filtering residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue, then ball milling in ball mill, again it is being adopted pressure compaction, put in clean ceramic crucible, in 400-500 DEG C of constant temperature 2-6h in air atmosphere, it is warming up at 850 DEG C again to be incubated after 10h and is slowly cooled to room temperature, sample comminution after firing, grind, cross 400 mesh sieves, obtain the nickel-cobalt lithium manganate cathode material that chemical property is good；
Step (5): solution crystallization in crystallizing evaporator that step (4) is filtrated to get, cerium sulphate crystal condition be vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains sodium sulfate, it is thus achieved that sodium sulfate return in step (2) and use.
The present invention compared with prior art has the advantage that cost is low, purification process non-secondary pollution produce are raw that effective cost is low, nickel cobalt manganese lithium reclaims of easy operation, antacid tail gas clean-up.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
As it is shown in figure 1, the present invention utilizes useless nickle cobalt lithium manganate to purify antacid tail gas the method reclaiming nickel cobalt manganese lithium, the steps include:
Step (1): collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 1-3h in sodium hydrate aqueous solution；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Collect and make, with nickle cobalt lithium manganate, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；The positive plate obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5-1h from room temperature, then naturally cool to room temperature；Taking out through the positive plate of roasting, put into by positive plate equipped with filling in the container of water and stirring 5-30min, sieved by the mixture screen cloth in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and makes furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；
Step (2): mixed with sodium sulfate by useless nickle cobalt lithium manganate, then ball milling in ball mill, load the mixture after ball milling in absorption plant；Mixture after loading ball milling in the identical absorption plant of another one uses in step (3) as standby absorption plant；In this step, the source of sodium sulfate is the sodium sulfate or the two mixture being mixed to form with arbitrary proportion that obtain in the sodium sulfate chemical products or step (5) bought；
Step (3): from gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into equipped with the conversion system of vanadium catalyst carries out conversion operation again, the condition of conversion operation is: gasinlet temperature 400-405 DEG C, flow velocity 0.23-1.2m/s, in conversion system, the filling of vanadium catalyst is rated for: 0.3-0.6m3Catalyst/(1000m3Antacid tail gas h)；From conversion system gas out pass into described in step (2) have been charged into ball milling after mixture absorption plant carry out absorption operation, the condition of absorption operation is: temperature 300-450 DEG C, inlet gas flow velocity 0.2-1.2m/s；SO in monitoring absorption plant exit gas2Content whether lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, as reached requirement, discharge to air after the gas cooling that absorption plant is exported；As monitored SO in absorption plant exit gas2Content reach 400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then no longer pass into from conversion system gas out in this absorption plant, by passing into from conversion system gas out, the standby absorption plant described in step (2) carry out the absorption operation under the same terms and SO in exit gas simultaneously2Content, sulfuric acid mist the monitoring of content；Taking out the mixture in the absorption plant no longer passing into conversion system exit gas in this step, the mixture that this absorption plant then returns to after being again loaded into ball milling in step (2) uses in this step as standby absorption plant；
Step (4): being leached with the water of 20-50 DEG C when stirring by the mixture in the absorption plant no longer passing into conversion system exit gas in step (3), extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate being warmed up to 95-98 DEG C, sodium carbonate liquor is slowly added to leachate, then filter, washing filtering residue also dries, and analyzes the content of Ni, Co, Mn in filtering residue, then supplements nickelous carbonate (NiCO toward filtering residue3), cobalt carbonate (CoCO3), manganese carbonate (MnCO3) in one or both, make the Ni in filtering residue after supplementing, Co, Mn mol ratio meets the requirement of 1:1:1, analyze Li in filtering residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue, then ball milling in ball mill, again it is being adopted pressure compaction, put in clean ceramic crucible, in 400-500 DEG C of constant temperature 2-6h in air atmosphere, it is warming up at 850 DEG C again to be incubated after 10h and is slowly cooled to room temperature, sample comminution after firing, grind, cross 400 mesh sieves, obtain the nickel-cobalt lithium manganate cathode material that chemical property is good；
Step (5): solution crystallization in crystallizing evaporator that step (4) is filtrated to get, cerium sulphate crystal condition be vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains sodium sulfate, it is thus achieved that sodium sulfate return in step (2) and use.
The concentration of the sodium hydrate aqueous solution in the step (1) of approach described above is 0.1-1.0mol/L.
The positive plate of acquisition is 1:10-1:15 in the ratio g/mL of the quality of positive plate Yu the volume of ceramic crucible by the step (1) of approach described above.
The step (1) of approach described above is 1:40-1:70 according to the ratio g/mL of the quality of positive plate Yu the volume of water, positive plate is put into equipped with filling in the container of water and stirring 5-30min with motor stirrer, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min.
The screen cloth that screen cloth is 10-20 order in the step (1) of approach described above.
Being mixed with the ratio that sodium sulfate g/g in mass ratio is 1:0.01-2.2 by the useless nickle cobalt lithium manganate obtained in the step (2) of approach described above, then ball milling in ball mill, Ball-milling Time is 0.1-1.0h, and rotating speed is 200-500r/min.
In the step (4) of approach described above, the concentration of sodium carbonate liquor is 1.0-3.0mol/L.
Ball-milling Time in the step (4) of approach described above is 0.5-2h, and rotating speed is 200-500r/min, and the pressure of compression is 0.1-100MPa.
Vanadium catalyst in the step (3) of approach described above is S108 type vanadium catalyst.
The present invention is further spread out below by embodiment.It it is only the better embodiment to the present invention described in embodiment, not the present invention is done any pro forma restriction, the every any simple modification embodiment of embodiment done according to the technical spirit of the present invention, equivalent variations and modification, belong in the scope of technical solution of the present invention.
Embodiment 1:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:0.1 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 2:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:0.3 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 410 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 3:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:0.5 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 390 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 4:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:0.7 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 5:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:0.9 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 415 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 6:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:1.1 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 7:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:1.3 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 420 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 8:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:1.5 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 415 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 9:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:1.7 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 380 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 10:
Collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 2h in the sodium hydrate aqueous solution of 0.5mol/L；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible in the ratio that the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible is 1:10 by the positive plate obtained, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:1.9 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 11:
Collect and make, with nickle cobalt lithium manganate, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:10 in the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:2.0 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 410 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 12:
Collect and make, with nickle cobalt lithium manganate, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:10 in the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:1.4 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 405 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 13:
Collect and make, with nickle cobalt lithium manganate, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:10 in the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:1.0 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 395 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 14:
Collect and make, with nickle cobalt lithium manganate, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:10 in the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:0.6 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 400 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 425 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Embodiment 15:
Collect and make, with nickle cobalt lithium manganate, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；Positive plate is loaded in ceramic crucible by the ratio being 1:10 in the ratio (g/mL) of the quality of positive plate Yu the volume of ceramic crucible, it is subsequently placed in chamber type electric resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5h from room temperature, after power-off, naturally cool to room temperature；Take out the positive plate through roasting, positive plate put into equipped with filling in the container of water and stirring 20min with motor stirrer according to the ratio (g/mL) of the volume of quality and the water of positive plate for 1:50, in whipping process, the temperature of water is 25 DEG C, and mixing speed is 100r/min；After stopping stirring, being sieved by the screen cloth of 10 orders of the mixture in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 3 times, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in chamber type electric resistance furnace and makes furnace temperature be raised to 550 DEG C and be incubated 1h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；The useless nickle cobalt lithium manganate ratio that (g/g) is 1:0.8 in mass ratio with sodium sulfate being mixed, then ball milling in planetary ball mill, Ball-milling Time is 0.5h, and rotating speed is 300r/min；Mixture after ball milling loads in absorption plant；From gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into again and the conversion system equipped with S108 type vanadium catalyst carries out conversion operation, the condition of conversion operation is: gasinlet temperature 405 DEG C, flow velocity 0.3m/s, in conversion system, the filling of S108 type vanadium catalyst is rated for: 0.5m3Catalyst/(1000m3Antacid tail gas h)；Passing into from conversion system gas out and carry out absorption operation the absorption plant of mixture after having been charged into ball milling, the condition of absorption operation is: temperature 400 DEG C, inlet gas flow velocity 0.3m/s；SO in absorption plant exit gas detected2Content lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, discharge to air after the gas cooling that absorption plant is exported；Mixture in the absorption plant no longer passing into conversion system exit gas is leached 20min with solid-to-liquid ratio (g/mL) for 1:20 with the water of 40 DEG C when stirring；nullThen leachate is warmed up to 98 DEG C，The sodium carbonate liquor of 3.0mol/L is slowly added to leachate，Filtering residue is through filtering、Washing、After drying，Analyze Ni in filtering residue、Co、The content of Mn，In filtering residue, supplement appropriate manganese carbonate make Ni in filtering residue、Co、Mn mol ratio reaches the requirement of 1:1:1，Analyze Li in filtering residue again、Ni、Co、The content of Mn，According to Li、Ni、Co、The requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue，Then with the abundant ball milling 2h of the speed of 400r/min in planetary ball mill，Again that it is tight at the pressure of 5MPa，Put in clean ceramic crucible，In 450 DEG C of constant temperature 4h in air atmosphere，It is slowly cooled to room temperature after being warming up to 850 DEG C of insulation 10h again，Sample after firing is size-reduced、Grind，Cross 400 mesh sieves，Obtain nickel-cobalt lithium manganate cathode material；The solution crystallization in crystallizing evaporator that will be filtrated to get, cerium sulphate crystal condition is vacuum 0.015MPa, temperature 120 DEG C, and crystal is dry under 80 DEG C and 2h obtains sodium sulfate.
Claims (9)
1. utilize useless nickle cobalt lithium manganate to purify antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterised in that the steps include:
Step (1): collect the scrap lithium ion battery doing positive electrode with nickle cobalt lithium manganate, be at room temperature positioned over the discharge process carrying out 1-3h in sodium hydrate aqueous solution；After discharge process, the lithium ion battery scrapped is disassembled, it is thus achieved that positive plate；Collect and make, with nickle cobalt lithium manganate, the positive pole leftover pieces that the lithium ion battery manufacture process of positive electrode produces, it is thus achieved that positive plate；The positive plate obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and starts to make with the heating rate of 5 DEG C/min furnace temperature be raised to 550 DEG C of insulation 0.5-1h from room temperature, then naturally cool to room temperature；Taking out through the positive plate of roasting, put into by positive plate equipped with filling in the container of water and stirring 5-30min, sieved by the mixture screen cloth in container, oversize is aluminium foil, and siftage is the solution containing positive active material；Siftage carries out sucking filtration, and in filter, thing use water cleans 1-3 time, it is thus achieved that positive active material；The positive active material obtained is loaded in ceramic crucible, is subsequently placed in resistance furnace and makes furnace temperature be raised to 500-700 DEG C and be incubated 0.5-3h with the heating rate of 5 DEG C/min, it is thus achieved that useless nickle cobalt lithium manganate；
Step (2): mixed with sodium sulfate by useless nickle cobalt lithium manganate, then ball milling in ball mill, load the mixture after ball milling in absorption plant；Mixture after loading ball milling in the identical absorption plant of another one uses in step (3) as standby absorption plant；In this step, the source of sodium sulfate is the sodium sulfate or the two mixture being mixed to form with arbitrary proportion that obtain in the sodium sulfate chemical products or step (5) bought；
Step (3): from gas washing in SA production double-absorption system antacid tail gas out, after first passing through heat treated, pass into equipped with the conversion system of vanadium catalyst carries out conversion operation again, the condition of conversion operation is: gasinlet temperature 400-405 DEG C, flow velocity 0.23-1.2m/s, in conversion system, the filling of vanadium catalyst is rated for: 0.3-0.6m3Catalyst/(1000m3Antacid tail gas h)；From conversion system gas out pass into described in step (2) have been charged into ball milling after mixture absorption plant carry out absorption operation, the condition of absorption operation is: temperature 300-450 DEG C, inlet gas flow velocity 0.2-1.2m/s；SO in monitoring absorption plant exit gas2Content whether lower than 400mg/m3And whether the content of sulfuric acid mist is lower than 30mg/m3, as reached requirement, discharge to air after the gas cooling that absorption plant is exported；As monitored SO in absorption plant exit gas2Content reach 400mg/m3Or the content of sulfuric acid mist reaches 30mg/m3, then no longer pass into from conversion system gas out in this absorption plant, by passing into from conversion system gas out, the standby absorption plant described in step (2) carry out the absorption operation under the same terms and SO in exit gas simultaneously2Content, sulfuric acid mist the monitoring of content；Taking out the mixture in the absorption plant no longer passing into conversion system exit gas in this step, the mixture that this absorption plant then returns to after being again loaded into ball milling in step (2) uses in this step as standby absorption plant；
Step (4): being leached with the water of 20-50 DEG C when stirring by the mixture in the absorption plant no longer passing into conversion system exit gas in step (3), extraction time 5-30min, solid-to-liquid ratio g/mL is 1:10-1:50；Then leachate being warmed up to 95-98 DEG C, sodium carbonate liquor is slowly added to leachate, then filter, washing filtering residue also dries, and analyzes the content of Ni, Co, Mn in filtering residue, then supplements nickelous carbonate (NiCO toward filtering residue3), cobalt carbonate (CoCO3), manganese carbonate (MnCO3) in one or both, make the Ni in filtering residue after supplementing, Co, Mn mol ratio meets the requirement of 1:1:1, analyze Li in filtering residue again, Ni, Co, the content of Mn, according to Li, Ni, Co, the requirement that the mol ratio of Mn is 1.05:0.33:0.33:0.33 supplements a certain amount of lithium carbonate toward filtering residue, then ball milling in ball mill, again it is being adopted pressure compaction, put in clean ceramic crucible, in 400-500 DEG C of constant temperature 2-6h in air atmosphere, it is warming up at 850 DEG C again to be incubated after 10h and is slowly cooled to room temperature, sample comminution after firing, grind, cross 400 mesh sieves, obtain the nickel-cobalt lithium manganate cathode material that chemical property is good；
Step (5): solution crystallization in crystallizing evaporator that step (4) is filtrated to get, cerium sulphate crystal condition be vacuum 0.012-0.015MPa, temperature 120-140 DEG C, crystal is dry under 50-80 DEG C and 0.2-3h obtains sodium sulfate, it is thus achieved that sodium sulfate return in step (2) and use.
2. the useless nickle cobalt lithium manganate of utilization according to claim 1 purifies antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterised in that: the concentration of the sodium hydrate aqueous solution in step (1) is 0.1-1.0mol/L.
3. the useless nickle cobalt lithium manganate of utilization according to claim 1 purifies antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterised in that: the positive plate of acquisition is 1:10-1:15 in the ratio g/mL of the quality of positive plate Yu the volume of ceramic crucible by step (1).
4. the useless nickle cobalt lithium manganate of utilization according to claim 1 purifies antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterized in that: step (1) is 1:40-1:70 according to the ratio g/mL of the quality of positive plate Yu the volume of water, positive plate is put into equipped with filling in the container of water and stirring 5-30min with motor stirrer, in whipping process, the temperature of water is 20-50 DEG C, and mixing speed is 10-200r/min.
5. the useless nickle cobalt lithium manganate of utilization according to claim 1 purifies antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterised in that: the screen cloth that screen cloth is 10-20 order in step (1).
6. the useless nickle cobalt lithium manganate of utilization according to claim 1 purifies antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterized in that: the useless nickle cobalt lithium manganate obtained is mixed by step (2) with the ratio that sodium sulfate g/g in mass ratio is 1:0.01-2.2, then ball milling in ball mill, Ball-milling Time is 0.1-1.0h, and rotating speed is 200-500r/min.
7. the useless nickle cobalt lithium manganate of utilization according to claim 1 purifies antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterised in that: in step (4), the concentration of sodium carbonate liquor is 1.0-3.0mol/L.
8. the useless nickle cobalt lithium manganate of utilization according to claim 1 purifies antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterised in that: the Ball-milling Time in step (4) is 0.5-2h, and rotating speed is 200-500r/min, and the pressure of compression is 0.1-100MPa.
9. the useless nickle cobalt lithium manganate of utilization according to claim 1 purifies antacid tail gas the method reclaiming nickel cobalt manganese lithium, it is characterised in that: the vanadium catalyst in step (3) is S108 type vanadium catalyst.
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