CN108183207A - A kind of method that compound manganese ore prepares anode material of lithium battery - Google Patents
A kind of method that compound manganese ore prepares anode material of lithium battery Download PDFInfo
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- CN108183207A CN108183207A CN201711409650.1A CN201711409650A CN108183207A CN 108183207 A CN108183207 A CN 108183207A CN 201711409650 A CN201711409650 A CN 201711409650A CN 108183207 A CN108183207 A CN 108183207A
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
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- 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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of method that compound manganese ore prepares anode material of lithium battery, the compound manganese ore is mainly made of manganese sulfide and manganese oxide, wherein vulcanization manganese content is 70% ~ 75%, oxidation manganese content is 10% ~ 15%, and the composition of the positive electrode is：LixCo0.25Mn0.7V0.3Oy/ C, wherein x=1 ~ 2, y=2 ~ 4, the specific steps of the method include：Compound manganese ore and sulfuric acid solution are placed in progress automatic oxidation reduction leaching in reactor；Oxidant is added in reactor and carries out Oxidation Leaching, filtering, the leachate containing manganese sulfate is obtained stoichiometrically cobaltous sulfate, vanadic sulfate and manganese sulfate are dissolved in deionized water, it adds in ammonium hydroxide and sodium hydroxide solution evaporates moisture to colloidal sol, colloidal sol is placed in Muffle furnace and is passed through argon gas heating, presoma is made；Presoma and lithium carbonate are mixed in proportion, calcined to obtain the positive electrode.Prepare that anode material of lithium battery is efficient, at low cost, and charge-discharge performance is good by method provided by the invention.
Description
Technical field
The invention belongs to a kind of methods that battery technology field more particularly to compound manganese ore prepare anode material of lithium battery.
Background technology
Manganese metal is to prepare the indispensable metallic element of anode material of lithium battery.In the prior art, lithium battery is prepared just
Pole material needs to purchase the raw material containing manganese of high-purity so that cost is higher.
The mode of production of manganese metal uses electrolysis at present.Electrolytic manganese metal is to obtain sulfuric acid through Ore Leaching with manganese ore
Manganese, then the elemental metals that electrolyzer electric is sent to parse.The production method of existing manganese sulfate solution is：Manganese ore is broken with crusher
It is broken, pulverize, then troilite powder is prepared according to a certain percentage with manganese mineral powder, add water, plus sulfuric acid.Reacted by heating,
Except manganese sulfate solution is made in iron, removing heavy metals, neutralization, press filtration.But this traditional handicraft there are manganese recovery ratio it is low the problem of.
Therefore, it is necessary to provide a kind of preparation method of novel anode material of lithium battery.
Apply for content
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, are provided a kind of multiple
The method that manganese ore prepares anode material of lithium battery is closed, is asked with solving existing anode material of lithium battery preparation process technology of high cost
Topic.
In order to solve the above technical problems, technical solution proposed by the present invention is：A kind of compound manganese ore prepares lithium battery anode
The method of material, the compound manganese ore are mainly made of manganese sulfide and manganese oxide, wherein vulcanization manganese content is 70% ~ 75%, oxygen
It is 10% ~ 10% to change manganese content, and the composition of the positive electrode is：LixCo0.25Mn0.7V0.3Oy/ C, wherein x=1 ~ 2, y=2 ~
4, the specific steps of the method include：
（1）Compound manganese ore and sulfuric acid solution are placed in reactor to the addition for carrying out automatic oxidation reduction leaching, wherein sulfuric acid solution
Amount and the weight ratio of compound manganese ore are 2~10: 1, and extraction temperature is 40 DEG C ~ 100 DEG C, and extraction time is 40min ~ 120min；
（2）Oxidant is added in into the step（1）Reactor in carry out Oxidation Leaching, filter, obtain the leaching containing manganese sulfate
Go out liquid and the leached mud containing elemental sulfur；
（3）To the step（2）In obtained leachate clean, manganese sulfate is precipitated after dry；
（4）Stoichiometrically by cobaltous sulfate, vanadic sulfate and the step（3）The manganese sulfate of middle preparation is dissolved in deionized water,
A concentration of 2.5 ~ 3mol/L, stirs evenly, and then adds in reaction kettle, adds in ammonium hydroxide and sodium hydroxide solution adjusts pH value and reaches
10 ~ 10.5, moisture is evaporated in 60 ~ 80 DEG C of water-bath to colloidal sol, is cooled to room temperature, colloidal sol is placed in Muffle furnace is passed through later
Argon gas heats, until being completely dried, presoma is made；
（5）By the step（4）The presoma of middle preparation is mixed in proportion with lithium carbonate, is calcined to obtain the anode
Material.
Preferably, the composition of the positive electrode is：Li1.5Co0.25Mn0.7V0.3O4/ C.
Preferably, by the step（3）Specially：
In the step（2）In in obtained leachate, add in hydrogen peroxide and remove iron tramp in solution, reserved filtrate；In the filter
Sulphurizing salt heavy-metal ion removal is added in liquid, it is 4.5 ~ 5.0 to adjust pH value, and manganese sulfate is precipitated after filtering, drying.
Preferably, the step（5）It specifically includes：
Presoma and lithium carbonate are mixed in proportion, 2 ~ 3h of pre-burning at 550 ~ 600 DEG C, furnace cooling is ground after cooling；
8 ~ 9h is calcined at 850 ~ 900 DEG C again, furnace cooling continues to grind after cooling；
2 ~ 3h is finally calcined at 950 ~ 1000 DEG C, natural cooling is ground after cooling, is sieved, is obtained the positive electrode.
Preferably, it further includes：
By the step（2）In obtained leached mud add in desulfurizing agent and obtain desulfurization slag and the solvent containing elemental sulfur, will contain
The solvent for having elemental sulfur cools down, and simple substance Sulfur releasing therein is made to obtain elemental sulfur product.
Preferably, the desulfurizing agent is kerosene, carbon tetrachloride or ammonium sulfide, and desulfurization temperature is 120 DEG C~180 DEG C.
Preferably, in the step（1）It further includes before：
Compound manganese ore is crushed, is ground, magnetic separation, it is less than the compound manganese ore of 150 purposes to obtain granularity.
Preferably, it is described to be ground to carry out high speed grinding using planetary ball mill.
Preferably, the step（1）In, it is opposite to the compound manganese ore and sulphur that automatic oxidation reduction leaching is carried out in reactor
Acid solution is stirred, and mixing speed is 200r/min ~ 1000r/min, H in the sulfuric acid solution+A concentration of 1.0mol/L
~8mol/L, and oxidant or reducing agent are not added in automatic oxidation reduction leaching process.
Preferably, the step（2）In oxidant for oxygen, the oxygen partial pressure is 0.15 ~ 0.5MPa.
Compared with prior art, the advantage of the invention is that：
（1）The present invention provides for mainly by the compound manganese ore that manganese sulfide and manganese oxide form using method, this is directly purchased
Compound manganese ore prepares anode material of lithium battery, at low cost；
（2）Using method provided by the present invention, the present invention utilizes the chemical characteristic of manganese sulfide and manganese oxide, by autoxidation also
Original reaction, you can manganese sulfate is made, avoids titanium dioxide caused by roasting manganese glance when extracting manganese metal in the prior art
The pollution of sulphur；
（3）During realizing automatic oxidation reduction reaction, it is only necessary to add in sulfuric acid solution, step is simple, at low cost.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments, for those of ordinary skill in the art, without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the process flow chart that the compound manganese ore of the present invention prepares anode material of lithium battery.
Specific embodiment
For the ease of understanding the present invention, done more entirely below in conjunction with Figure of description and preferred embodiment to inventing herein
Face meticulously describes, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
The present invention provides a kind of method that compound manganese ore prepares anode material of lithium battery, the compound manganese ore is mainly by sulphur
Change manganese and manganese oxide composition, wherein vulcanization manganese content is 70% ~ 75%, oxidation manganese content is 10% ~ 15%, the positive electrode
Composition be：LixCo0.25M0.7V0.3Oy/ C, wherein x=1 ~ 2, y=2 ~ 4.Preferably, the positive electrode is：
Li1.5Co0.25Mn0.7V0.3O4/ C.
Embodiment 1,
Referring to Fig. 1, a kind of method that compound manganese ore prepares anode material of lithium battery, specific steps include：
Compound manganese ore and sulfuric acid solution be placed in reactor progress automatic oxidation reduction leaching by step S1, wherein sulfuric acid solution
The weight ratio of addition and compound manganese ore is 2 ~ 10: 1, and extraction temperature is 40 DEG C~100 DEG C, extraction time for 40min~
120min；
Specifically, compound manganese ore is crushed using planetary ball mill, high speed grinding, magnetic separation, it is to be less than to obtain granularity
The compound manganese ore of 150 purposes.
By the compound manganese ores of 100g and H+The sulfuric acid solution 900ml of a concentration of 4mol/L is placed in reactor and carries out autoxidation also
Original leaches, and is stirred with 500r/min mixing speeds, and extraction temperature is 90 DEG C, extraction time 60min.
Due to containing a large amount of manganese sulfides in compound manganese ore, following react occurs in step sl:
MnO2+MnS+2H2SO4=2MnSO4+2H2O+S。
Oxidant is added in the reactor of the step S1 and carries out Oxidation Leaching by step S2, and filtering is obtained containing sulfuric acid
The leachate of manganese and the leached mud containing elemental sulfur；
Specifically, oxygen is passed through into reactor, under the conditions of constant temperature, permanent partial pressure of oxygen, it is small to leach 3 by oxygen partial pressure 0.15MPa
When.
Following react occurs in step s 2：
2MnS+2H2SO4+O2=2MnSO4+2H2O+2S。
The leached mud obtained in the step S2 is added in the kerosene of 400ml, is warmed to 150 DEG C, constant temperature 60min.Reaction
It finishes, pours out upper strata load elemental sulfur kerosene, then washing desulphurization slag is three times, the kerosene that elemental sulfur kerosene will be loaded with wash sulphur
Merge, be cooled to room temperature, and filter, obtain elemental sulfur product.
Step S3 cleans to the leachate obtained in the step S2, and manganese sulfate is precipitated after dry；
Specifically, in the leachate obtained in the step S2, the iron tramp in hydrogen peroxide reaction 1h removing solution is added in, is stayed
Filtrate；Sulphurizing salt heavy-metal ion removal is added in the filtrate, it is 4.8 to adjust pH value, and manganese sulfate is precipitated after filtering, drying.
Step S4, stoichiometrically by the manganese sulfate prepared in cobaltous sulfate, vanadic sulfate and the step S3 be dissolved in from
In sub- water, a concentration of 2.8mol/L is stirred evenly, and is then added in reaction kettle, adds in ammonium hydroxide and sodium hydroxide solution adjusts pH
Value reaches 10.5, and moisture is evaporated in 70 DEG C of water-bath to colloidal sol, is cooled to room temperature, colloidal sol is placed in Muffle furnace is passed through later
Argon gas heats, until being completely dried, presoma is made；
Step S5 mixes in proportion the presoma prepared in the step S4 with lithium carbonate, is calcined to obtain described
Positive electrode.
Specifically, presoma and lithium carbonate are mixed in proportion, the pre-burning 2h at 580 DEG C, furnace cooling, after cooling
Grinding；
8h is calcined at 870 DEG C again, furnace cooling continues to grind after cooling；
2.5h is finally calcined at 970 DEG C, natural cooling is ground after cooling, and sieving obtains the positive electrode.
By above-mentioned material by being assembled into battery after, reach 140mAh/g, 3.8V in 7mA/g current density discharge capacities
Using upper mounting plate rate as 94.0%, using identical test method, LiCoO2The discharge capacity and platform rate of the lithium battery of material be
131mAh/g and 86.7%.
Embodiment 2
A kind of method that compound manganese ore prepares anode material of lithium battery, specific steps include：
Compound manganese ore is crushed using planetary ball mill, high speed grinding, magnetic separation, it is less than 150 purposes to obtain granularity
Compound manganese ore.By the compound manganese ores of 1kg and H+The sulfuric acid solution 3L of a concentration of 1mol/L, which is placed in reactor, carries out automatic oxidation reduction
It leaches, is stirred with 200r/min mixing speeds, extraction temperature is 40 DEG C, extraction time 120min；
Oxygen is passed through into reactor, oxygen partial pressure 0.3MPa under the conditions of constant temperature, permanent partial pressure of oxygen, is leached 2 hours.Filtering,
Obtain the leachate containing manganese sulfate and the leached mud containing elemental sulfur；
Leached mud is added in the carbon tetrachloride of 400ml, is warmed to 180 DEG C, constant temperature 60min.Reaction finishes, and pours out upper strata load
Elemental sulfur carbon tetrachloride, then washing desulphurization slag is three times, will load elemental sulfur carbon tetrachloride and merges with washing the carbon tetrachloride of sulphur, it is cold
But it to room temperature, and filters, obtains elemental sulfur product.
In leachate, the iron tramp in hydrogen peroxide reaction 1h removing solution, reserved filtrate are added in；Sulphur is added in the filtrate
Salt dissolving heavy-metal ion removal, it is 4.8 to adjust pH value, and manganese sulfate is precipitated after filtering, drying.
Stoichiometrically cobaltous sulfate, vanadic sulfate and manganese sulfate are dissolved in deionized water, a concentration of 3mol/L, stirring is equal
It is even, it then adds in reaction kettle, adds in ammonium hydroxide and sodium hydroxide solution adjusts pH value and reaches 10.5, evaporated in 70 DEG C of water-bath
Moisture is cooled to room temperature to colloidal sol, colloidal sol is placed in Muffle furnace is passed through argon gas heating later, until being completely dried, before being made
Drive body；
Presoma and lithium carbonate are mixed in proportion,
The pre-burning 2.5h at 550 DEG C, furnace cooling are ground after cooling；
8.5h is calcined at 850 DEG C again, furnace cooling continues to grind after cooling；
2h is finally calcined at 950 DEG C, natural cooling is ground after cooling, and sieving obtains the positive electrode.
By above-mentioned material by being assembled into battery after, reach 138mAh/g, 3.8V in 7mA/g current density discharge capacities
Using upper mounting plate rate as 93.0%, using identical test method, LiCoO2The discharge capacity and platform rate of the lithium battery of material be
131mAh/g and 86.7%.
Embodiment 3
A kind of method that compound manganese ore prepares anode material of lithium battery, specific steps include：
Compound manganese ore is crushed using planetary ball mill, high speed grinding, magnetic separation, it is less than 150 purposes to obtain granularity
Compound manganese ore.By the compound manganese ores of 200g and H+The sulfuric acid solution 200ml of a concentration of 8mol/L, which is placed in reactor, carries out autoxidation
Reducing leaching is stirred with 1000r/min mixing speeds, and extraction temperature is 100 DEG C, extraction time 40min；
Oxygen is passed through into reactor, oxygen partial pressure 0.5MPa under the conditions of constant temperature, permanent partial pressure of oxygen, is leached 2 hours.Filtering,
Obtain the leachate containing ammonium sulfide and the leached mud containing elemental sulfur；
Leached mud is added in the ammonium sulfide of 400ml, is warmed to 120 DEG C, constant temperature 60min.Reaction finishes, and it is single to pour out upper strata load
Matter sulfur vulcanization ammonium, then washing desulphurization slag is three times, will load vulcanization of elemental sulfur ammonium and merges with washing the ammonium sulfide of sulphur, is cooled to room
Temperature, and filter, obtain elemental sulfur product.
In leachate, the iron tramp in hydrogen peroxide reaction 1h removing solution, reserved filtrate are added in；Sulphur is added in the filtrate
Salt dissolving heavy-metal ion removal, it is 4.8 to adjust pH value, and manganese sulfate is precipitated after filtering, drying.
Stoichiometrically cobaltous sulfate, vanadic sulfate and manganese sulfate are dissolved in deionized water, a concentration of 2.5mol/L, stirred
Uniformly, it then adds in reaction kettle, adds in ammonium hydroxide and sodium hydroxide solution adjusts pH value and reaches 10.3, steamed in 80 DEG C of water-bath
Shampoo point is cooled to room temperature to colloidal sol, colloidal sol is placed in Muffle furnace is passed through argon gas heating later, until being completely dried, be made
Presoma；
Presoma and lithium carbonate are mixed in proportion,
The pre-burning 9h at 600 DEG C, furnace cooling are ground after cooling；
9h is calcined at 900 DEG C again, furnace cooling continues to grind after cooling；
3h is finally calcined at 1000 DEG C, natural cooling is ground after cooling, and sieving obtains the positive electrode.
By above-mentioned material by being assembled into battery after, reach 142mAh/g, 3.8V in 7mA/g current density discharge capacities
Using upper mounting plate rate as 96.0%, using identical test method, LiCoO2The discharge capacity and platform rate of the lithium battery of material be
131mAh/g and 86.7%.
Claims (10)
1. a kind of method that compound manganese ore prepares anode material of lithium battery, which is characterized in that the compound manganese ore is mainly by vulcanizing
Manganese and manganese oxide composition, wherein vulcanization manganese content is 70% ~ 75%, oxidation manganese content is 10% ~ 15%, the positive electrode
It forms and is：LixCo0.25Mn0.7V0.3Oy/ C, wherein x=1 ~ 2, y=2 ~ 4, the specific steps of the method include：
（1）Compound manganese ore and sulfuric acid solution are placed in reactor to the addition for carrying out automatic oxidation reduction leaching, wherein sulfuric acid solution
Amount and the weight ratio of compound manganese ore are 2 ~ 10: 1, and extraction temperature is 40 DEG C ~ 100 DEG C, and extraction time is 40min~120min；
（2）Oxidant is added in into the step（1）Reactor in carry out Oxidation Leaching, filter, obtain the leaching containing manganese sulfate
Go out liquid and the leached mud containing elemental sulfur；
（3）To the step（2）In obtained leachate clean, manganese sulfate is precipitated after dry；
（4）Stoichiometrically by cobaltous sulfate, vanadic sulfate and the step（3）The manganese sulfate of middle preparation is dissolved in deionized water,
A concentration of 2.5 ~ 3mol/L, stirs evenly, and then adds in reaction kettle, adds in ammonium hydroxide and sodium hydroxide solution adjusts pH value and reaches
10 ~ 10.5, moisture is evaporated in 60 ~ 80 DEG C of water-bath to colloidal sol, is cooled to room temperature, colloidal sol is placed in Muffle furnace is passed through later
Argon gas heats, until being completely dried, presoma is made；
（5）By the step（4）The presoma of middle preparation is mixed in proportion with lithium carbonate, is calcined to obtain the anode
Material.
2. the method that compound manganese ore according to claim 1 prepares anode material of lithium battery, which is characterized in that the anode
The composition of material is：Li1.5Co0.25Mn0.7V0.3O4/ C.
3. the method that compound manganese ore according to claim 1 prepares anode material of lithium battery, which is characterized in that by the step
Suddenly（3）Specially：
In the step（2）In in obtained leachate, add in hydrogen peroxide and remove iron tramp in solution, reserved filtrate；In the filter
Sulphurizing salt heavy-metal ion removal is added in liquid, it is 4.5 ~ 5.0 to adjust pH value, and manganese sulfate is precipitated after filtering, drying.
4. the method that compound manganese ore according to claim 1 prepares anode material of lithium battery, which is characterized in that the step
（5）It specifically includes：
Presoma and lithium carbonate are mixed in proportion, 2 ~ 3h of pre-burning at 550 ~ 600 DEG C, furnace cooling is ground after cooling；
8 ~ 9h is calcined at 850 ~ 900 DEG C again, furnace cooling continues to grind after cooling；
2 ~ 3h is finally calcined at 950 ~ 1000 DEG C, natural cooling is ground after cooling, is sieved, is obtained the positive electrode.
5. the method that compound manganese ore according to claim 1 prepares anode material of lithium battery, which is characterized in that further include：
By the step（2）In obtained leached mud add in desulfurizing agent, obtain desulfurization slag and the solvent containing elemental sulfur, will contain
The solvent for having elemental sulfur cools down, and simple substance Sulfur releasing therein is made to obtain elemental sulfur product.
6. the method that compound manganese ore according to claim 5 prepares anode material of lithium battery, which is characterized in that the desulfurization
Agent is kerosene, carbon tetrachloride or ammonium sulfide, and desulfurization temperature is 120 DEG C ~ 180 DEG C.
7. the method that compound manganese ore according to claim 1 prepares anode material of lithium battery, which is characterized in that in the step
Suddenly（1）It further includes before：
Compound manganese ore is crushed, is ground, magnetic separation, it is less than the compound manganese ore of 150 purposes to obtain granularity.
8. the method that compound manganese ore according to claim 7 prepares anode material of lithium battery, which is characterized in that the grinding
To carry out high speed grinding using planetary ball mill.
9. the method that compound manganese ore according to claim 1 prepares anode material of lithium battery, which is characterized in that the step
（1）In, it is opposite to the compound manganese ore of progress automatic oxidation reduction leaching and sulfuric acid solution in reactor and is stirred, mixing speed is
200r/min ~ 1000r/min, H in the sulfuric acid solution+A concentration of 1.0mol/L ~ 8mol/L, and automatic oxidation reduction leached
Oxidant or reducing agent are not added in journey.
10. the method that compound manganese ore according to claim 1 prepares anode material of lithium battery, which is characterized in that the step
Suddenly（2）In oxidant for oxygen, the oxygen partial pressure is 0.15 ~ 0.5MPa.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113860385A (en) * | 2021-10-09 | 2021-12-31 | 四川天人能源科技有限公司 | Recycling method of ferro-manganese desulfurizer solid waste |
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