CN103594697B - A kind of method being prepared manganate cathode material for lithium by potassium permanganate manganese waste slag - Google Patents
A kind of method being prepared manganate cathode material for lithium by potassium permanganate manganese waste slag Download PDFInfo
- Publication number
- CN103594697B CN103594697B CN201310557995.7A CN201310557995A CN103594697B CN 103594697 B CN103594697 B CN 103594697B CN 201310557995 A CN201310557995 A CN 201310557995A CN 103594697 B CN103594697 B CN 103594697B
- Authority
- CN
- China
- Prior art keywords
- manganese
- potassium permanganate
- lithium
- hydrochloric acid
- waste slag
- 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.)
- Active
Links
- 239000012286 potassium permanganate Substances 0.000 title claims abstract description 74
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011572 manganese Substances 0.000 title claims abstract description 69
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 68
- 239000002699 waste material Substances 0.000 title claims abstract description 63
- 239000002893 slag Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 50
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 39
- 239000010406 cathode material Substances 0.000 title claims abstract description 24
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 35
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 35
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 35
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 35
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 8
- 238000010671 solid-state reaction Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 88
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 18
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000011565 manganese chloride Substances 0.000 claims description 18
- 235000002867 manganese chloride Nutrition 0.000 claims description 18
- 229940099607 manganese chloride Drugs 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000003836 solid-state method Methods 0.000 claims description 8
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 5
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 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
- 239000000463 material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1207—Permanganates ([MnO]4-) or manganates ([MnO4]2-)
- C01G45/1214—Permanganates ([MnO]4-) or manganates ([MnO4]2-) containing alkali metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of method being prepared manganate cathode material for lithium by potassium permanganate manganese waste slag, described method comprises the steps: that potassium permanganate manganese waste slag is obtained manganese carbonate through ionic reaction by (1); (2) gained manganese carbonate is mixed with lithium source, carry out high temperature solid state reaction, prepare manganate cathode material for lithium.The invention provides a kind of new way of process potassium permanganate manganese waste slag of novelty, can turn waste into wealth, solve the pollution problem of potassium permanganate manganese waste slag to environment, improve utilance and the added value of potassium permanganate manganese waste slag.
Description
Technical field
The invention belongs to electrochemical power source technical field of material, particularly relate to a kind of method being prepared manganate cathode material for lithium by potassium permanganate waste residue.
Background technology
Potassium permanganate is widely used in medicine, chemical industry, metallurgy, environmental protection etc. industry.World's potassium permanganate yearly productive capacity is more than 80,000 tons, but the waste residue environmental pollution of producing potassium permanganate generation is serious.Do not have production 1 ton of potassium permanganate can produce the manganese waste slag of 0.4 ton, and most employing pile of existing manganese waste slag or land-fill method do temporary transient process, add the expense such as enterprise's land acquisition and place disposal, add production cost, consume land resource, and long-term storage causes serious environmental pollution.
The manganese waste slag producing potassium permanganate generation is interior main containing manganese dioxide, silicon dioxide, di-iron trioxide, the total potassium of dissolving with hydrochloric acid, alundum (Al2O3), calcium oxide, magnesium oxide, water-soluble value Mn etc., and therefore these manganese waste slags are actually a kind of secondary resource.But, simple and easy stacking or landfill are taked to potassium permanganate waste residue, and again do not utilize, and do not take the control measures such as any antiseepage, sealing and percolate process, easily cause the wasting of resources, environmental pollution.Therefore how to potassium permanganate waste reside comprehensive utilization, be a research direction of those skilled in the art.
Therefore, this area needs a kind of secondary utilization method producing the manganese waste slag that potassium permanganate produces badly.
Summary of the invention
An object of the present invention is a kind of method providing potassium permanganate manganese waste slag secondary to utilize, described method utilizes potassium permanganate manganese waste slag, extract manganese carbonate, manganate cathode material for lithium is obtained by reacting with lithium source, the secondary achieving potassium permanganate manganese waste slag utilizes, improve its utilance, solve the pollution problem of potassium permanganate manganese waste slag to environment.
The present invention is achieved through the following technical solutions:
Prepared a method for manganate cathode material for lithium by potassium permanganate manganese waste slag, comprise the steps:
(1) potassium permanganate manganese waste slag is obtained manganese carbonate through ionic reaction;
(2) gained manganese carbonate is mixed with lithium source, carry out high temperature solid state reaction, prepare manganate cathode material for lithium.
Potassium permanganate manganese waste slag of the present invention produces the waste residue of discharging in potassium permanganate process.
Preferably, described potassium permanganate manganese waste slag mainly containing manganese dioxide, potassium permanganate, solubility salt, silicate and metal oxide, the combination of any a kind or at least 2 kinds in the metal chosen from Fe of described metal oxide, magnesium, calcium or aluminium;
Preferably, in described potassium permanganate manganese waste slag, manganese dioxide accounts for 35 ~ 45% of potassium permanganate manganese waste slag total weight, as 37%, 39%, 43%, 44% etc., potassium permanganate accounts for 3 ~ 7% of potassium permanganate waste residue total weight, and such as 3.1%, 3.9%, 4.4%, 4.8%, 5.5%, 6.4%, 6.8% etc.
Step of the present invention (1) described ionic reaction comprises the steps:
(1a) roughly select: get potassium permanganate manganese waste slag, add water, cross and filter potassium permanganate and solubility salt, obtain filter residue I;
(1b) add watery hydrochloric acid: in filter residue I, add watery hydrochloric acid, leave standstill, filter, obtain filter residue II;
(1c) extract manganese: in filter residue II, add concentrated hydrochloric acid, leave standstill, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: in manganese chloride filtrate, add sodium carbonate, obtain manganese carbonate precipitation, after through washing, after oven dry manganese carbonate.
Wherein, temperature≤35 DEG C of watery hydrochloric acid in step (1b), such as 18 DEG C, 22 DEG C, 27 DEG C, 32 DEG C etc., preferably 10 ~ 30 DEG C; The concentration of described watery hydrochloric acid is preferably 1 ~ 3mol/L.
Preferably, in step (1c), the temperature of concentrated hydrochloric acid is 50 ~ 70 DEG C, preferably 58.4 DEG C; The concentration of described concentrated hydrochloric acid is preferably 12 ~ 13mol/L.
In the described ionic reaction process of step of the present invention (1), the addition of step (1a) described water is 5 ~ 10 times of potassium permanganate manganese waste slag quality, such as 6 times, 7 times, 8 times, 9 times etc., preferably 6 ~ 8 times.
Preferably, the addition of step (1b) described watery hydrochloric acid is 2 ~ 5 times of filter residue I quality, such as 2.2 times, 2.7 times, 3.2 times, 3.7 times, 4 times, 4.3 times, 4.8 times etc., preferably 2 ~ 4 times; The described standing time is preferably 0.5h ~ 3h, such as 0.6h, 0.8h, 1.2h, 1.6h, 1.8h, 2.3h, 2.6h, 2.9h etc., preferably 1 ~ 2h;
Preferably, the addition of step (1c) described concentrated hydrochloric acid is 2 ~ 5 times of filter residue II quality, such as 2.2 times, 2.7 times, 3.2 times, 3.7 times, 4 times, 4.3 times, 4.8 times etc., preferably 2 ~ 4 times; The described standing time is preferably 0.5h ~ 3h, such as 0.6h, 0.8h, 1.2h, 1.6h, 1.8h, 2.3h, 2.6h, 2.9h etc., preferably 1 ~ 2h.
Lithium source of the present invention is selected from the combination of any a kind or at least 2 kinds in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride, the combination of described combination such as lithium carbonate and lithium hydroxide, the combination of lithium oxalate and lithium chloride, the combination of lithium oxalate and lithium acetate, the combination etc. of lithium carbonate, lithium hydroxide and lithium chloride.
In the described high temperature solid-state method reaction of step of the present invention (2), manganese carbonate and lithium source are the ratio mixing of 2:1 according to manganese element and elemental lithium mol ratio.
The temperature of high temperature solid-state method reaction of the present invention is 700 ~ 850 DEG C, such as 702 DEG C, 715 DEG C, 735 DEG C, 750 DEG C, 768 DEG C, 789 DEG C, 806 DEG C, 815 DEG C, 835 DEG C, 845 DEG C, 848 DEG C etc., reaction time is 15 ~ 25h, such as 16h, 17h, 19h, 21h, 22h, 24h etc.
Preferably, the temperature of described high temperature solid-state method reaction is 750 ~ 800 DEG C, and the reaction time is 18 ~ 22h.
As optimal technical scheme, prepared the method for manganate cathode material for lithium by potassium permanganate manganese waste slag, comprise the steps:
(1a) roughly select: get potassium permanganate manganese waste slag, add the water of manganese waste slag quality 5 ~ 10 times, cross and filter potassium permanganate and solubility salt, obtain filter residue I;
(1b) add watery hydrochloric acid: the concentration adding filter residue quality 2 ~ 5 times in filter residue I is the watery hydrochloric acid of 1 ~ 3mol/L, leave standstill 0.5 ~ 3h, filter, obtain filter residue II;
(1c) extract manganese: the concentration adding filter residue quality 2 ~ 5 times in filter residue II is the concentrated hydrochloric acid of 12 ~ 13mol/L, at 50 ~ 70 DEG C, leave standstill 0.5 ~ 3h, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: add sodium carbonate by manganese chloride filtrate, obtain manganese carbonate precipitation, be washed with water to pH value neutrality, after oven dry, namely obtain manganese carbonate.
(2) mixed with lithium source by gained manganese carbonate, in mixture, the mol ratio of manganese element and elemental lithium is that 2:1 carries out high temperature solid-state method reaction, prepares manganate cathode material for lithium.
Compared with prior art, the present invention has following beneficial effect:
The present invention utilizes potassium permanganate manganese waste slag, extract manganese carbonate, manganate cathode material for lithium is obtained by reacting with lithium source, the secondary achieving potassium permanganate manganese waste slag utilizes, provide a kind of new way of process potassium permanganate manganese waste slag of novelty, can turn waste into wealth, solve the pollution problem of potassium permanganate manganese waste slag to environment, improve utilance and the added value of potassium permanganate manganese waste slag.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
A kind of method preparing manganate cathode material for lithium by potassium permanganate manganese waste slag comprises the steps:
(1a) roughly select: get 1kg potassium permanganate manganese waste slag, add 10kg water, cross and filter potassium permanganate manganese and solubility salt, obtain 0.7kg filter residue I;
(1b) add watery hydrochloric acid: in filter residue I, add the watery hydrochloric acid that 1.4kg concentration is 1mol/L, 20 DEG C of standing 1h, filter, obtain 0.5kg filter residue II;
(1c) extract manganese: in filter residue II, add the concentrated hydrochloric acid that 1kg concentration is 12mol/L, 50 DEG C of standing 1h, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: add sodium carbonate by manganese chloride filtrate, obtain manganese carbonate precipitation, be washed with water to pH value neutrality, after oven dry, namely obtain manganese carbonate;
(2) get lithium carbonate to mix by lithium manganese element mol ratio 1:2 with the manganese carbonate that step (1d) obtains, roasting 15h at 700 DEG C, carry out high temperature solid state reaction, obtain LiMn2O4 compound, through grinding, sieve the manganate cathode material for lithium obtaining 400 ~ 700nm particle diameter.
Embodiment 2
A kind of method preparing manganate cathode material for lithium by potassium permanganate manganese waste slag comprises the steps:
(1a) roughly select: get 10kg potassium permanganate manganese waste slag, add 50kg water, cross and filter potassium permanganate manganese and solubility salt, obtain 4kg filter residue I;
(1b) add watery hydrochloric acid: in filter residue I, add the watery hydrochloric acid that 20kg concentration is 3mol/L, 30 DEG C of standing 0.5h, filter, obtain 3kg filter residue II;
(1c) extract manganese: in filter residue II, add the concentrated hydrochloric acid that 6kg concentration is 13mol/L, 70 DEG C of standing 0.5h, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: add sodium carbonate by manganese chloride filtrate, obtain manganese carbonate precipitation, be washed with water to pH value neutrality, after oven dry, namely obtain manganese carbonate;
(2) get lithium hydroxide to mix by lithium manganese element mol ratio 1:2 with the manganese carbonate that step (1d) obtains, roasting 18h at 750 DEG C, carry out high temperature solid state reaction, obtain LiMn2O4 compound, through grinding, sieve the manganate cathode material for lithium obtaining 600 ~ 1000nm particle diameter.
Embodiment 3
A kind of method preparing manganate cathode material for lithium by potassium permanganate manganese waste slag comprises the steps:
(1a) roughly select: get 10kg potassium permanganate manganese waste slag, add 70kg water, cross and filter potassium permanganate manganese and solubility salt, obtain 5kg filter residue I;
(1b) add watery hydrochloric acid: in filter residue I, add the watery hydrochloric acid that 15kg concentration is 1mol/L, 18 DEG C of standing 2.8h, filter, obtain 4kg filter residue II;
(1c) extract manganese: in filter residue II, add the concentrated hydrochloric acid that 16kg concentration is 12.5mol/L, 70 DEG C of standing 3h, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: add sodium carbonate by manganese chloride filtrate, obtain manganese carbonate precipitation, be washed with water to pH value neutrality, after oven dry, namely obtain manganese carbonate;
(2) get lithium oxalate to mix by lithium manganese element mol ratio 1:2 with the manganese carbonate that step (1d) obtains, roasting 10h at 780 DEG C, carry out high temperature solid state reaction, obtain LiMn2O4 compound, through grinding, sieve the manganate cathode material for lithium obtaining 800 ~ 1300nm particle diameter.
Embodiment 4
A kind of method preparing manganate cathode material for lithium by potassium permanganate manganese waste slag comprises the steps:
(1a) roughly select: get 10kg potassium permanganate manganese waste slag, add 80kg water, cross and filter potassium permanganate manganese and solubility salt, obtain 4.5kg filter residue I;
(1b) add watery hydrochloric acid: in filter residue I, add the watery hydrochloric acid that 11kg concentration is 2mol/L, 23 DEG C of standing 2h, filter, obtain 2kg filter residue II;
(1c) extract manganese: in filter residue II, add the concentrated hydrochloric acid that 18kg concentration is 13mol/L, 58.4 DEG C of standing 3h, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: add sodium carbonate by manganese chloride filtrate, obtain manganese carbonate precipitation, be washed with water to pH value neutrality, after oven dry, namely obtain manganese carbonate;
(2) lithium oxalate is got and lithium acetate mixes by lithium manganese element mol ratio 1:2 with the manganese carbonate that step (1d) obtains, roasting 22h at 800 DEG C, carry out high temperature solid state reaction, obtain LiMn2O4 compound, through grinding, sieve the manganate cathode material for lithium obtaining 800 ~ 1300nm particle diameter.
Embodiment 5
A kind of method preparing manganate cathode material for lithium by potassium permanganate manganese waste slag comprises the steps:
(1a) roughly select: get 10kg potassium permanganate manganese waste slag, add 60kg water, cross and filter potassium permanganate manganese and solubility salt, obtain 5.3kg filter residue I;
(1b) add watery hydrochloric acid: in filter residue I, add the watery hydrochloric acid that 20kg concentration is 1.5mol/L, 27 DEG C of standing 2h, filter, obtain 4kg filter residue II;
(1c) extract manganese: in filter residue II, add the concentrated hydrochloric acid that 21kg concentration is 12.8mol/L, 60 DEG C of standing 2h, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: add sodium carbonate by manganese chloride filtrate, obtain manganese carbonate precipitation, be washed with water to pH value neutrality, after oven dry, namely obtain manganese carbonate;
(2) get lithium chloride to mix by lithium manganese element mol ratio 1:2 with the manganese carbonate that step (1d) obtains, roasting 25h at 850 DEG C, carry out high temperature solid state reaction, obtain LiMn2O4 compound, through grinding, sieve the manganate cathode material for lithium obtaining 900 ~ 1100nm particle diameter.
It should be noted that and understand, when not departing from the spirit and scope of the present invention required by accompanying claim, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (23)
1. prepared a method for manganate cathode material for lithium by potassium permanganate manganese waste slag, it is characterized in that,
Described method comprises the steps:
(1) potassium permanganate manganese waste slag is obtained manganese carbonate through ionic reaction;
(2) gained manganese carbonate is mixed with lithium source, carry out high temperature solid state reaction, prepare manganate cathode material for lithium;
Described potassium permanganate manganese waste slag produces the waste residue of discharging in potassium permanganate process; Described potassium permanganate manganese waste slag mainly containing manganese dioxide, potassium permanganate, silicate, metal oxide and other soluble-salt classes, the combination of any a kind or at least 2 kinds in the metal chosen from Fe of described metal oxide, magnesium, calcium or aluminium;
Step (1) described ionic reaction comprises the steps:
(1a) roughly select: get potassium permanganate manganese waste slag, add water, cross and filter potassium permanganate and the solubility salt except potassium permanganate, obtain filter residue I;
(1b) add watery hydrochloric acid: in filter residue I, add watery hydrochloric acid, leave standstill, filter, obtain filter residue II;
(1c) extract manganese: in filter residue II, add concentrated hydrochloric acid, leave standstill, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: in manganese chloride filtrate, add sodium carbonate, obtain manganese carbonate precipitation, after through washing, after oven dry manganese carbonate.
2. the method for claim 1, is characterized in that, in described potassium permanganate manganese waste slag, manganese dioxide accounts for 35 ~ 45% of potassium permanganate manganese waste slag total weight, and potassium permanganate accounts for 3 ~ 7% of potassium permanganate manganese waste slag total weight.
3. the method for claim 1, is characterized in that, temperature≤35 DEG C of watery hydrochloric acid in step (1b).
4. method as claimed in claim 3, is characterized in that, the temperature 10 ~ 30 DEG C of watery hydrochloric acid in step (1b).
5. the method for claim 1, is characterized in that, the concentration of step (1b) described watery hydrochloric acid is 1 ~ 3mol/L.
6. the method for claim 1, is characterized in that, in step (1c), the temperature of concentrated hydrochloric acid is 50 ~ 70 DEG C.
7. method as claimed in claim 6, is characterized in that, in step (1c), the temperature of concentrated hydrochloric acid is 58.4 DEG C.
8. the method for claim 1, is characterized in that, the concentration of described concentrated hydrochloric acid is 12 ~ 13mol/L.
9. the method for claim 1, is characterized in that, the addition of step (1a) described water is 5 ~ 10 times of potassium permanganate manganese waste slag quality.
10. method as claimed in claim 9, it is characterized in that, the addition of step (1a) described water is 6 ~ 8 times of potassium permanganate manganese waste slag quality.
11. the method for claim 1, is characterized in that, the addition of step (1b) described watery hydrochloric acid is 2 ~ 5 times of filter residue I quality.
12. methods as claimed in claim 11, is characterized in that, the addition of step (1b) described watery hydrochloric acid is 2 ~ 4 times of filter residue I quality.
13. the method for claim 1, is characterized in that, step (1b) the described standing time is 0.5h ~ 3h.
14. methods as claimed in claim 13, is characterized in that, step (1b) the described standing time is 1 ~ 2h.
15. the method for claim 1, is characterized in that, the addition of step (1c) described concentrated hydrochloric acid is 2 ~ 5 times of filter residue II quality.
16. methods as claimed in claim 15, is characterized in that, the addition of step (1c) described concentrated hydrochloric acid is 2 ~ 4 times of filter residue II quality.
17. the method for claim 1, is characterized in that, step (1c) the described standing time is 0.5h ~ 3h.
18. methods as claimed in claim 17, is characterized in that, step (1c) the described standing time is 1 ~ 2h.
19. the method for claim 1, is characterized in that, described lithium source is selected from the combination of any a kind or at least 2 kinds in lithium carbonate, lithium hydroxide, lithium oxalate, lithium acetate, lithium chloride.
20. the method for claim 1, is characterized in that, in the described high temperature solid-state method reaction of step (2), manganese carbonate and lithium source are the ratio mixing of 2:1 according to manganese element and elemental lithium mol ratio.
21. the method for claim 1, is characterized in that, the temperature of described high temperature solid-state method reaction is 700 ~ 850 DEG C, and the reaction time is 15 ~ 25h.
22. the method for claim 1, is characterized in that, the temperature of described high temperature solid-state method reaction is 750 ~ 800 DEG C, and the reaction time is 18 ~ 22h.
23. the method for claim 1, is characterized in that, described method comprises the steps:
(1a) roughly select: get potassium permanganate manganese waste slag, add the water of manganese waste slag quality 5 ~ 10 times, cross and filter potassium permanganate and the solubility salt except potassium permanganate, obtain filter residue I;
(1b) add watery hydrochloric acid: the concentration adding filter residue quality 2 ~ 5 times in filter residue I is the watery hydrochloric acid of 1 ~ 3mol/L, leave standstill 0.5 ~ 3h, filter, obtain filter residue II;
(1c) extract manganese: the concentration adding filter residue quality 2 ~ 5 times in filter residue II is the concentrated hydrochloric acid of 12 ~ 13mol/L, at 50 ~ 70 DEG C, leave standstill 0.5 ~ 3h, filter, obtain manganese chloride filtrate;
(1d) add sodium carbonate: add sodium carbonate by manganese chloride filtrate, obtain manganese carbonate precipitation, be washed with water to pH value neutrality, after oven dry, namely obtain manganese carbonate;
(2) mixed with lithium source by gained manganese carbonate, in mixture, the mol ratio of manganese element and elemental lithium is that 2:1 carries out high temperature solid-state method reaction, prepares manganate cathode material for lithium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310557995.7A CN103594697B (en) | 2013-11-11 | 2013-11-11 | A kind of method being prepared manganate cathode material for lithium by potassium permanganate manganese waste slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310557995.7A CN103594697B (en) | 2013-11-11 | 2013-11-11 | A kind of method being prepared manganate cathode material for lithium by potassium permanganate manganese waste slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103594697A CN103594697A (en) | 2014-02-19 |
| CN103594697B true CN103594697B (en) | 2015-12-30 |
Family
ID=50084748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310557995.7A Active CN103594697B (en) | 2013-11-11 | 2013-11-11 | A kind of method being prepared manganate cathode material for lithium by potassium permanganate manganese waste slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103594697B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127726A (en) * | 1995-05-19 | 1996-07-31 | 赵培岭 | Method for producing manganese sulfate using waste residue from production of potassium permanganate |
| CN1166698A (en) * | 1997-01-17 | 1997-12-03 | 武汉大学 | Preparation method of anode material LiMn2O4 for high-performance lithium ion batteryh |
| CN1715254A (en) * | 2004-06-14 | 2006-01-04 | 杨迎艺 | Method for comprehensively treating and using waste slag from producing potassium permanganate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3753754B2 (en) * | 1995-01-26 | 2006-03-08 | 日本電工株式会社 | Method for producing spinel type LiMn2O4 |
-
2013
- 2013-11-11 CN CN201310557995.7A patent/CN103594697B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127726A (en) * | 1995-05-19 | 1996-07-31 | 赵培岭 | Method for producing manganese sulfate using waste residue from production of potassium permanganate |
| CN1166698A (en) * | 1997-01-17 | 1997-12-03 | 武汉大学 | Preparation method of anode material LiMn2O4 for high-performance lithium ion batteryh |
| CN1715254A (en) * | 2004-06-14 | 2006-01-04 | 杨迎艺 | Method for comprehensively treating and using waste slag from producing potassium permanganate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103594697A (en) | 2014-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103746111B (en) | A kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof | |
| CN103773966B (en) | The extraction and application method of neodymium iron boron waste material | |
| CN104805299B (en) | Method for preparing lithium battery electrode materials LiFePO4 and Li4Ti5O12 from vanadium extraction slag | |
| CN108987749A (en) | The method of ferric phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore | |
| CN103746115A (en) | Method for preparing cell-grade lithium iron phosphate from pyrite slag | |
| CN103979584B (en) | A kind of boric sludge is for Magnesium Carbonate Light 41-45 technique | |
| CN108238832B (en) | Method for preparing soluble potassium and calcium silicate soil conditioner by alkali-activated potassium feldspar | |
| CN104805302A (en) | Method for extracting vanadium and titanium from vanadium-containing titanium slag | |
| CN101552346A (en) | Method of preparing electrolyte of vanadium ion redox flow battery | |
| CN108584994A (en) | A kind of method of lepidolite calcined by rotary kiln lithium carbonate | |
| CN104577104B (en) | Regeneration method of positive material lithium manganate waste of lithium ion battery | |
| CN104600389A (en) | Method for recycling metal from spent lithium ion battery of lithium manganate anode material | |
| CN103022491A (en) | Method for preparing lithium iron phosphate precursor for positive pole material of lithium-ion battery | |
| CN105185993A (en) | Synthetic method for high-purity iron phosphate and doped metallic element thereof | |
| CN110240200A (en) | The method of tungsten is extracted from tungsten ore | |
| CN102328961A (en) | Precursor of nickel cobalt lithium manganate positive material for lithium ion battery and production method thereof | |
| CN114014294B (en) | Method for preparing lithium iron phosphate by using pyrite and lithium iron phosphate material | |
| CN103594696A (en) | Method for preparing surface-coated high-voltage positive electrode material of lithium ion battery | |
| CN109264691B (en) | Method for preparing lithium manganese iron phosphate from lithium iron phosphate | |
| CN102230072B (en) | Roasting method for extracting vanadium from vanadium-containing shale | |
| CN109928375A (en) | A method of ferric phosphate is prepared using calcium dihydrogen phosphate | |
| CN103594697B (en) | A kind of method being prepared manganate cathode material for lithium by potassium permanganate manganese waste slag | |
| CN104600284A (en) | Method for regenerating positive active material in spent lithium manganate lithium ion battery | |
| KR101957706B1 (en) | Recovering method of lithium from lithium-manganese oxide | |
| KR101466497B1 (en) | Method of recovering lithium from fly ashes or waste water derived from active material for lithium secondary battery by using electrochemisty process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method of using potassium permanganate waste residue to prepare lithium manganate cathode material Effective date of registration: 20161110 Granted publication date: 20151230 Pledgee: Gansu double credit Company limited by guarantee Pledgor: Gansu elephant Energy Technology Co., Ltd. Registration number: 2016620000025 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20170906 Granted publication date: 20151230 Pledgee: Gansu double credit Company limited by guarantee Pledgor: Gansu elephant Energy Technology Co., Ltd. Registration number: 2016620000025 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method of using potassium permanganate waste residue to prepare lithium manganate cathode material Effective date of registration: 20171213 Granted publication date: 20151230 Pledgee: Gansu double credit Company limited by guarantee Pledgor: Gansu elephant Energy Technology Co., Ltd. Registration number: 2017620000028 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20190813 Granted publication date: 20151230 Pledgee: Gansu double credit Company limited by guarantee Pledgor: Gansu elephant Energy Technology Co., Ltd. Registration number: 2017620000028 |