CN110078180A - A method of carbon coating composite oxide powder is prepared using stainless steel acid-washing waste liquid - Google Patents
A method of carbon coating composite oxide powder is prepared using stainless steel acid-washing waste liquid Download PDFInfo
- Publication number
- CN110078180A CN110078180A CN201910430458.3A CN201910430458A CN110078180A CN 110078180 A CN110078180 A CN 110078180A CN 201910430458 A CN201910430458 A CN 201910430458A CN 110078180 A CN110078180 A CN 110078180A
- Authority
- CN
- China
- Prior art keywords
- composite oxide
- oxide powder
- stainless steel
- waste liquid
- acid
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/52—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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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 methods using stainless steel acid-washing waste liquid preparation carbon coating composite oxide powder, belong to waste utilization field.A method of carbon coating composite oxide powder being prepared using stainless steel acid-washing waste liquid, the pH value of stainless steel acid-washing waste liquid is adjusted to 7~11 using solid base or aqueous slkali, mixes them thoroughly and generates the mixed liquor containing sediment；Filtering gained mixed liquor, and, in 400~700 DEG C of ball millings, composite oxide powder will be obtained after gained sediment drying；Dry after gained composite oxide powder is mixed with carbon source material, under argon atmosphere, 300~400 DEG C of ball millings react 0.5~4h, obtain carbon coating composite oxide powder.Harmful heavy metal ion is subjected to curing process and resource utilization while the present invention realizes stainless steel acid-washing waste liquid harmless discharge, obtains the composite negative pole material of lithium ion battery.
Description
Technical field
The present invention relates to a kind of methods using stainless steel acid-washing waste liquid preparation carbon coating composite oxide powder, belong to useless
Object utilizes field.
Background technique
Stainless steel in process of production, can inevitably be produced by process, surfaces such as punching press, annealing, flangings
Iron, manganese, the nickel, chromium oxide skin of raw black.These black dense oxides not only influence the appearance of stainless steel, can also add to subsequent
Work has an adverse effect, it is necessary to be removed using the surface treatment methods such as polishing, pickling.Wherein, to carry out pickling processes to it advantageous
In enhancing stainless steel corrosion resistance and improve stainless steel surface crystallinity, common pickling medium include hydrofluoric acid, nitric acid,
Hydrochloric acid, sulfuric acid etc..It can be generated after pickling and largely contain Cr3+、Ni2+、F-And the pickle liquor that acid ion is toxic, by
It is included in " National Hazard waste register ".
When sour using hydrochloric acid based solution as acid-washing stainless steel, pickle liquor includes acid ion and metal cation
(Cl-、Cr3+、Fe3+、Fe2+、Ni2+).Wherein iron, chromium, nickel are the metallic elements that there is higher reclamation to be worth, and pickle liquor is one
Kind can be with the precious resources of recycling and reusing.Pass through the Cr in recycling stainless steel acid-washing waste liquid3+、Ni2+、Fe3+、Fe2+, both solved
The pollution problem of heavy metal ion chromium, nickel, also achieves the Resources Strategy turned waste into wealth, obtains significant economic benefit.Root
According to the noxious pollutant of pickle liquor in stainless steel, current main methods have:
(1) Neutralisation treatment method is precipitated:
Currently, most of stainless steel enterprises generally use alkaline matter such as quick lime to come in neutralization precipitation processing acid cleaning process
Pickle liquor, the pH value by adjusting waste liquid promotes the harmful ion Cr in pickle liquor3+、Ni2+、Fe3+、Fe2+Precipitating
It is precipitated, the main pollution for reducing waste liquid and having suffered heavy metal chromium, nickel element.Its advantage is that it is at low cost, easy to operate, easily controllable,
The discharge standard of waste water can be reached；The disadvantage is that the sediment generated includes hydroxide, carbonate and extra lime,
The hydroxide precipitating of chromium, nickel can not be made therefrom to separate, will cause secondary pollution, i.e., a large amount of pickling sludge, and contain
The sludge of heavy metal ion does not have effective method direct utilization, needs to deliver environmental protection administration's special disposal and spends
A large amount of expense.
(2) sludge sub-prime neutralisation:
Chinese patent (CN 101269889A) discloses a kind of processing method of stainless steel acid cleaning waste water and liquid, first uses NaOH
Lye precipitates the metal cation in waste liquid, and lime is then added and obtains calcium fluoride precipitate, makes the metal sludge generated and fluorination
Object sludge separates.Although this processing method can be such that sludge quantity reduces, there is also obvious shortcomings: (1) adding medicament
NaOH lye cost is higher: (2) do not carry out all contaminated ions to integrate pollution-free disposition；(3) tail washings is processed into
This is costly.(4) the final resource utilization of polluted heavy metals ion is not solved the problems, such as.
(3) Chinese patent (CN 101863516A) is disclosed from stainless steel acid cleaning waste water, sludge recycling Ni ferrite containing chromium
Method.The technology is by stainless steel acid-washing waste liquid treated heavy metal pickling sludge, through processes such as mashing, pickling, alkalization
Prepare ferrite.Its advantage is that being not only able to achieve waste water harmless discharge, but also pickling recycling sludge can be utilized, reach economic ring
The recycling requirement of guarantor.But there is also some drawbacks: 1) preparing ferrite in the process also needs that a large amount of chemical reagent, economy is added
Difference；2) this method prepares ferrite complex procedures, and time-consuming and is not easy large-scale industrial production use.
In conclusion the common drawback of the processing technique of existing stainless steel acid-washing waste liquid is that do not have to stainless steel liquid waste processing
A whole set of scheme coherent, that operability is high, the level of resources utilization is high is formed, it is useless that traditional operating process only considered pickling
The precipitatingization processing of heavy metal ion, does not pay attention to the resource utilization for resulting heavy metal precipitation object, so that containing in liquid
There are the substance disposal costs of heavy metal ion higher, pollution caused by secondary emission is larger.
Since the mankind enter industrialization society, the consumption of fossil energy is extremely serious, along with the more and more exhausted of resource
More and more with consumption of fossil fuels, therefore, research safety, efficient, environmental-friendly new energy, are national governments and science
The topic that family all pays special attention to.And battery power conforms exactly to the new energy target that we are pursued.With common lead-acid battery,
Ambrose alloy battery and other conventional batteries are compared, and lithium ion battery is by current internationally recognized for ideal chemical energy source.Lithium from
Sub- battery has biggish capacitance, higher operating voltage, lesser volume, safe green environmental protection, longer service life
Advantage.The chemical property of lithium ion battery mainly determines by the electrode material of battery, the positive material of present lithium ion battery
Expect main cobalt acid lithium, LiMn2O4, LiFePO4 etc., and cathode material includes graphite, coke, transition metal oxide and interphase
Carbosphere Carbon Materials, wherein transition metal oxide theoretical specific capacity with higher and first charge-discharge are capable of forming
LiO reduces the advantages that bulk effect, and therefore, transition metal oxide is a big hot spot of present research lithium ion battery material.
Summary of the invention
The present invention adds alkali neutralization precipitation process by carrying out to the heavy metal ion in stainless steel acid-washing waste liquid, to remove acid
Heavy metal ion pollution toxic in waste liquid is washed, is obtained by filtration under hydroxide high temperature and is broken down into composite oxide powder,
The negative electrode material that lithium ion battery is prepared using it has been reached to polluted heavy metals ion Cr3+、Ni2+Recycling and reusing mesh
, it had not only protected environment but also the high value for realizing waste utilizes.
The present invention is directed to hydrochloric acid-base pickle liquor, and pickle liquor includes acid ion and metal cation (Cl-、Cr3+、Fe3 +、Fe2+、Ni2+).Firstly, adjusting the pH value of acid group solution by the way that alkali is added, precipitates metal ion with hydroxide form, obtain
To Cr (OH)3、Fe(OH)2、Fe(OH)3With Ni (OH)2Mixed sediment, filtered filtrate are overregulated pH and a remaining huge sum of money
Meet the standard of sewage discharge after category ionic adsorption.Mixed sediment is placed in ball mill, is broken down at high temperature multiple
Close oxide powder.Gained powder uses carbon source solution (glucose, sucrose, citric acid, malic acid, ethyl alcohol or polyethylene glycol water
Solution) or graphene powder progress carbon coating processing, it then heats, mixing, grinding, obtains in the high energy ball milling machine of argon gas protection
Obtain micron order composite cathode material for lithium ion cell (Cr2O3-C、Fe2O3-C,NiO-C).Prepared composite negative pole material is crossed
As the cathode of battery on Cu platinum, other suitable battery materials such as anode material, diaphragm, electrolyte, binder etc. are chosen,
Finally it is assembled into the lithium ion battery that negative electrode material is composite transition metal oxide.By electrochemical property test, the lithium from
Sub- battery theoretical capacity with higher and coulombic efficiency (90% or more), after 100 cycle charge-discharges capacity be maintained at 400~
The advantages that 600mAh/g, charge and discharge volume change is small.
Technical solution of the present invention is as follows:
A method of carbon coating composite oxide powder being prepared using stainless steel acid-washing waste liquid, the method includes following
Processing step:
Step 1, the pH value of stainless steel acid-washing waste liquid is adjusted to 7~11 using solid base or aqueous slkali, mixed them thoroughly
And generate the mixed liquor containing sediment；
Step 2,1 gained mixed liquor of filtration step, and, in 400~700 DEG C of ball millings, will be obtained compound after gained sediment drying
Oxide powder；
Step 3, dry after step 2 gained composite oxide powder being mixed with carbon source material, under argon atmosphere, 300~
400 DEG C of ball millings react 0.5~4h, obtain carbon coating composite oxide powder.
Stainless steel acid-washing waste liquid of the present invention is hydrochloric acid-base stainless steel acid-washing waste liquid, which includes acid ion
Cl-、H+With metal cation Cr3+、Fe3+、Fe2+、Ni2+。
In above-mentioned technical proposal, stainless steel acid-washing waste liquid metal cation described in the step 1 is Cr3+、Fe3+、Fe2+、
Ni2+, after being adjusted using solid base or aqueous slkali, metal cation Cr3+、Fe3+、Fe2+、Ni2+It precipitates, finally obtains
Contain Cr (OH)3、Fe(OH)2、Fe(OH)3With Ni (OH)2The mixed liquor of mixed sediment.
The present invention will guarantee that the pH value of solution is higher than Cr after aqueous slkali is added3+、Fe3+、Fe2+、Ni2+Each ion precipitation
The 5%~10% of maximum ph can be such that various metal ions sufficiently precipitate in this way.
Further, the solid base is preferably sodium hydroxide, sodium carbonate, sodium bicarbonate；Aqueous slkali is ammonium hydroxide, needs to select
At least one of the above.
In above-mentioned technical proposal, in the step 2, mixed sediment and filtrate is obtained by filtration in mixed liquor.
In above-mentioned steps 2, gained filtrate is alkaline filtrate, and obtained alkaline filtrate is neutralized using acid, is remaining
It is discharged after meeting the standard of waste discharge after heavy metal ion adsorbed processing.
In above-mentioned steps 2, mixed sediment is placed in ball mill and carries out ball milling, is allowed to the hot conditions at 400~700 DEG C
Under be decomposed to form Cr2O3、Fe2O3With NiO composite oxides.
Ball mill used in the present invention has heating function, can be by adding resistive heater reality outside ball mill crucible
It is existing, and controlling heating temperature by temperature sensor etc. is required temperature.
Preferably, in the step 2, gained sediment drying is placed in ball mill, in 400~700 DEG C of ball millings 0.5
~6h, ball mill ratio of grinding media to material 10:1~20:1,60~80rpm of drum's speed of rotation.
In above-mentioned technical proposal, in the step 3, by step 2 gained Cr2O3、Fe2O3Carbon is carried out with NiO composite oxides
Cladding, finally obtains Cr2O3-C、Fe2O3- C, NiO-C cladded type composite granule.
Carbon coating of the present invention is realized by following techniques: step 2 gained composite oxide powder is mixed with carbon source material
Dry after conjunction, under argon atmosphere, 300~400 DEG C of ball millings react 0.5~4h, obtain carbon coating composite oxide powder.
Further, the carbon source material is that glucose, sucrose, citric acid, malic acid, ethyl alcohol or polyethylene glycol are water-soluble
Liquid or graphene powder.
Further, when carbon source material is glucose, sucrose, citric acid, malic acid, ethyl alcohol or Aqueous Solutions of Polyethylene Glycol
When, it is dry after step 2 gained composite oxide powder is mixed with carbon source material, under argon atmosphere, gained powder is placed in ball
In grinding machine, in 300~400 DEG C of 0.5~4h of ball milling, ball mill ratio of grinding media to material 10:1~20:1,60~80rpm of drum's speed of rotation.
Further, when carbon source material is graphene powder, under argon atmosphere, by graphene powder and combined oxidation
Gained powder is placed in ball mill after powder mixing, 0.5~4h of ball milling at room temperature~150 DEG C, ball mill ratio of grinding media to material 10:1
~20:1,60~80rpm of drum's speed of rotation.
It is a further object of the present invention to provide carbon coating composite oxide powders made from the above method as lithium-ion electric
The application of pond negative electrode material.
Further, prepared carbon coating composite oxide powder is coated on the cathode on Cu foil as battery, choosing
Other suitable battery materials such as positive electrode, diaphragm, electrolyte, binder etc. are taken, it is compound for being finally assembled into negative electrode material
The lithium ion battery of transition metal oxide.
The invention has the benefit that
(1) the method for the invention considers Cr in recycling and reusing stainless steel acid-washing waste liquid comprehensively3+、Fe3+、Fe2+、Ni2+,
Innoxious, solidification, recycling treatment are carried out, the utility value of toxic heavy metal ion is improved, obtains higher economy
Benefit；(2) by treated, tail washings realizes harmless discharge, protects environment；(3) sodium carbonate, carbonic acid are added in precipitation process
Hydrogen sodium, ammonium hydroxide can replace part NaOH, reduce production cost；(4) high energy ball milling is used in pyrolytic and carbonisation
Machine, simplification of flowsheet.
Harmful heavy metal ion is solidified while the present invention realizes stainless steel acid-washing waste liquid harmless discharge
Processing and resource utilization, obtain the composite negative pole material of lithium ion battery, not only increase the electrochemistry of lithium ion battery
Can, and make heavy metal ion Cr3+、Ni2+Resource utilization is carried out, prevents secondary pollution from generating.This invention has significant
Economical, society, environmental benefit, can be widely applied to the fields such as metallurgy and chemical industry and electrochemistry, have apparent innovative, preceding
Looking forward or upwards property and practicality.
Detailed description of the invention
Fig. 1 is a kind of process flow chart that lithium ion battery negative material is prepared using stainless steel acid-washing waste liquid.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Ball mill used is known as high energy ball milling machine in following embodiments, is twined on the outside of commercially available ball mill crucible
Obtained by resistive heater, while it being equipped with corresponding power supply and temperature control device, there is heating function and function of temperature control.
Embodiment 1
(1) by the pickle liquor obtained after acid-washing stainless steel (containing H+、Cl-、Cr3+、Fe3+、Fe2+、Ni2+) use mass ratio
For the solid NuaO and sodium carbonate mixture of 3:1, to be adjusted to pH value be 7, realizes Cr3+、Fe3+、Fe2+、Ni2+Ion is coprecipitated
It forms sediment, obtains Cr (OH) after filtering3、Fe(OH)2、Fe(OH)3、Ni(OH)2Mixed sediment and weakly alkaline filtrate, by institute
Obtained filtrate is added hydrochloric acid and is neutralized, while in filtrate modified bentonite is added (southern exposure, which moistens eastern produce sale, to be had
Limit company) as adsorbent for heavy metal progress residual heavy metal ionic adsorption processing, the standard of waste discharge to be met
Afterwards, it is discharged by drainage system.
(2) mixed sediment obtained after filtration drying is placed in high energy ball milling machine, is heated to 400 DEG C, control is high
The revolving speed of warm ball mill is 60rpm, and selection ratio of grinding media to material is 20:1, keeps the temperature 0.5h, is broken down into Cr2O3、Fe2O3, NiO mixing
Powder, 1.5 μm of granularity.Micron order composite oxide powder material is prepared using the heating, mixing, abrasive action in high energy ball milling machine
Material.
(3) composite oxide powder carbon coating processing use glucose solution, using when glucose solution first by carbon source material
Material (glucose) is dissolved in deionized water, is then mixed with combined oxidation powder, is packed into high energy ball milling machine after drying at 80 DEG C
In.It is passed through argon gas protection, and temperature is risen to 300 DEG C, 0.5h is reacted, obtains composite cathode material for lithium ion cell (Cr2O3-C、
Fe2O3-C、NiO-C)。
(4) prepared composite negative pole material is crossed in Cu foil as the cathode of battery, chooses other suitable battery materials
Material such as positive electrode (LiFePO4), diaphragm (polyethylene (PE) microporous barrier), electrolyte (LiBF4Organic solution), binder it is (poly-
Vinylidene (PVDF)) etc., finally it is assembled into the lithium ion battery that negative electrode material is composite transition metal oxide.It is close in electric current
It spends under the conditions of 100mAh/g, constant current charge-discharge test is carried out within the scope of 0.02~3V of voltage, as voltage is down to 0.02V, battery
First discharge specific capacity be 717.3mAh/g, initial charge specific capacity is 449.7mAh/g, should after 150 charge and discharge cycles
The specific capacity of electrode material is 465.5mAh/g.
Embodiment 2
(1) by the pickle liquor obtained after acid-washing stainless steel (containing H+、Cl-、Cr3+、Fe3+、Fe2+、Ni2+) use mass ratio
For the solid NuaO and sodium carbonate mixture of 3:1, to be adjusted to pH value be 8, realizes Cr3+、Fe3+、Fe2+、Ni2+Ion is coprecipitated
It forms sediment, obtains Cr (OH) after filtering3、Fe(OH)2、Fe(OH)3、Ni(OH)2Mixed sediment and weakly alkaline filtrate, by institute
Obtained filtrate is added hydrochloric acid and is neutralized, while in filtrate modified bentonite is added (southern exposure, which moistens eastern produce sale, to be had
Limit company) as adsorbent for heavy metal progress residual heavy metal ionic adsorption processing, the standard of waste discharge to be met
Afterwards, it is discharged by drainage system.
(2) mixed sediment obtained after filtration drying is placed in high energy ball milling machine, is heated to 500 DEG C, control is high
The revolving speed of warm ball mill is 70rpm, and selection ratio of grinding media to material is 15:1, keeps the temperature 2h, is broken down into Cr2O3、Fe2O3, NiO mixed powder
Body, 1.2 μm of granularity.Micron order composite oxide powder material is prepared using the heating, mixing, abrasive action in high energy ball milling machine
Material.
(3) composite oxide powder carbon coating, which is handled, can be used sucrose solution, using existing by carbon source material (sugarcane when solution
Sugar) it is dissolved in deionized water, it then mixes with combined oxidation powder, is fitted into high energy ball milling machine after being dried at 80 DEG C.It is passed through
Argon gas protection, and temperature is risen to 330 DEG C, 1.5h is reacted, composite cathode material for lithium ion cell (Cr is obtained2O3-C、Fe2O3-
C、NiO-C)。
(4) prepared composite negative pole material is crossed into the cathode on Cu foil as battery, chooses other suitable batteries
Material such as positive electrode (cobalt acid lithium), diaphragm (polyethylene (PE) microporous barrier), electrolyte (LiPF6Organic solution), binder it is (poly-
Vinylidene (PVDF)) etc., finally it is assembled into the lithium ion battery that negative electrode material is composite transition metal oxide.It is close in electric current
It spends under the conditions of 100mAh/g, constant current charge-discharge test is carried out within the scope of 0.02~3V of voltage, as voltage is down to 0.02V, battery
First discharge specific capacity be 758.3mAh/g, initial charge specific capacity is 470.1mAh/g, should after 150 charge and discharge cycles
The specific capacity of electrode material is 485.8mAh/g.
Embodiment 3
(1) by the pickle liquor obtained after acid-washing stainless steel (containing H+、Cl-、Cr3+、Fe3+、Fe2+、Ni2+) use mass ratio
Solid NuaO and concentration for 10:3 are that be adjusted to pH value be 9 to the mixture that is formed of 10% ammonium hydroxide, realize Cr3+、Fe3+、Fe2 +、Ni2+Ion co-precipitation, obtains Cr (OH) after filtering3、Fe(OH)2、Fe(OH)3、Ni(OH)2Mixed sediment and weak base
Property filtrate, obtained filtrate addition sulfuric acid is neutralized, while modified bentonite (southern exposure profit is added in filtrate
Eastern produce sell Co., Ltd) processing of residual heavy metal ionic adsorption is carried out as adsorbent for heavy metal, it is discarded wait meet
After the standard of object discharge, it is discharged by drainage system.
(2) mixed sediment obtained after filtration drying is placed in high energy ball milling machine, is heated to 550 DEG C, control is high
The revolving speed of warm ball mill is 80rpm, and selection ratio of grinding media to material is 10:1, keeps the temperature 3h, is broken down into Cr2O3、Fe2O3, NiO mixed powder
Body, 0.9 μm of granularity.Micron order composite oxide powder material is prepared using the heating, mixing, abrasive action in high energy ball milling machine
Material.
(3) composite oxide powder carbon coating, which is handled, can be used citric acid solution, using existing by carbon source when citric acid solution
Material (citric acid) is dissolved in deionized water, is then mixed with combined oxidation powder, is packed into high energy ball milling after drying at 80 DEG C
In machine.It is passed through argon gas protection, and temperature is risen to 350 DEG C, 2h is reacted, obtains composite cathode material for lithium ion cell (Cr2O3-C、
Fe2O3-C、NiO-C)。
(4) prepared composite negative pole material is crossed into the cathode on Cu foil as battery, chooses other suitable batteries
Material such as positive electrode (lithium nickelate), diaphragm (polyethylene (PE) microporous barrier), electrolyte (LiPF6Organic solution), binder it is (poly-
Vinylidene (PVDF)) etc., finally it is assembled into the lithium ion battery that negative electrode material is composite transition metal oxide.It is close in electric current
It spends under the conditions of 100mAh/g, constant current charge-discharge test is carried out within the scope of 0.02~3V of voltage, as voltage is down to 0.02V, battery
First discharge specific capacity be 856.2mAh/g, initial charge specific capacity is 530.4mAh/g, should after 150 charge and discharge cycles
The specific capacity of electrode material is 518.5mAh/g.
Embodiment 4
(1) by the pickle liquor obtained after acid-washing stainless steel (containing H+、Cl-、Cr3+、Fe3+、Fe2+、Ni2+) use mass ratio
For the solid NuaO and sodium carbonate mixture of 3:1, to be adjusted to pH value be 11, realizes Cr3+、Fe3+、Fe2+、Ni2+Ion is coprecipitated
It forms sediment, obtains Cr (OH) after filtering3、Fe(OH)2、Fe(OH)3、Ni(OH)2Mixed sediment and weakly alkaline filtrate, by institute
Obtained filtrate is added sulfuric acid and is neutralized, while in filtrate modified bentonite is added (southern exposure, which moistens eastern produce sale, to be had
Limit company) as adsorbent for heavy metal progress residual heavy metal ionic adsorption processing, the standard of waste discharge to be met
Afterwards, it is discharged by drainage system.
(2) mixed sediment obtained after filtration drying is placed in high energy ball milling machine, is heated to 600 DEG C, control is high
The revolving speed of warm ball mill is 75rpm, and selection ratio of grinding media to material is 15:1, keeps the temperature 4h, is broken down into Cr2O3、Fe2O3, NiO mixed powder
Body, 1 μm of granularity.Micron order composite oxide powder material is prepared using the heating, mixing, abrasive action in high energy ball milling machine.
(3) composite oxide powder carbon coating, which is handled, can be used graphene powder.Carbon coating is carried out using graphene powder
When can directly by graphene be packed into ball grinder and be passed through argon gas protection, at 70 DEG C carry out low-temperature mixed 3h, obtain lithium-ion electric
Pond composite negative pole material (Cr2O3-C、Fe2O3-C、NiO-C)。
(4) prepared composite negative pole material is crossed into the cathode on Cu foil as battery, chooses other suitable batteries
Material such as positive electrode (cobalt acid lithium), diaphragm (polyethylene (PE) microporous barrier), electrolyte (LiBF4Organic solution), binder it is (poly-
Vinylidene (PVDF)) etc., finally it is assembled into the lithium ion battery that negative electrode material is composite transition metal oxide.It is close in electric current
It spends under the conditions of 100mAh/g, constant current charge-discharge test is carried out within the scope of 0.02~3V of voltage, as voltage is down to 0.02V, battery
First discharge specific capacity be 822.3mAh/g, initial charge specific capacity is 500.7mAh/g, should after 150 charge and discharge cycles
The specific capacity of electrode material is 485.5mAh/g.
Embodiment 5
(1) by the pickle liquor obtained after acid-washing stainless steel (containing H+、Cl-、Cr3+、Fe3+、Fe2+、Ni2+) use mass ratio
For the solid NuaO, sodium carbonate, sodium bicarbonate mixture of 3:1:1, to be adjusted to pH value be 9, realizes Cr3+、Fe3+、Fe2+、Ni2+
Ion co-precipitation, obtains Cr (OH) after filtering3、Fe(OH)2、Fe(OH)3、Ni(OH)2Mixed sediment and weakly alkaline filter
Liquid neutralizes obtained filtrate addition hydrochloric acid, while modified bentonite (the eastern produce of southern exposure profit being added in filtrate
Sell Co., Ltd) processing of residual heavy metal ionic adsorption, waste discharge to be met are carried out as adsorbent for heavy metal
Standard after, be discharged by drainage system.
(2) sediment obtained after filtration drying is placed in high energy ball milling machine, is heated to 600 DEG C, control high temperature ball
The revolving speed of grinding machine is 65rpm, and selection ratio of grinding media to material is 10:1, keeps the temperature 6h, is broken down into Cr2O3、Fe2O3, NiO mixed powder, grain
1.1 μm of degree.Micron order composite oxide powder material is prepared using the heating, mixing, abrasive action in high energy ball milling machine.
(3) composite oxide powder carbon coating, which is handled, can be used Aqueous Solutions of Polyethylene Glycol, and graphene powder also can be used.Make
Carbon source material (polyethylene glycol) is dissolved in deionized water with existing when solution, is then mixed with combined oxidation powder, at 80 DEG C
It is fitted into after drying in high energy ball milling machine.It is passed through argon gas protection, and temperature is risen to 400 DEG C, 4h is reacted, it is multiple to obtain lithium ion battery
Close negative electrode material (Cr2O3-C、Fe2O3-C、NiO-C)。
(4) prepared composite negative pole material is crossed into the cathode on Cu foil as battery, chooses other suitable batteries
Material such as positive electrode (LiFePO4), diaphragm (polyethylene (PE) microporous barrier), electrolyte (LiAsF6Organic solution), binder
(Kynoar (PVDF)) etc. is finally assembled into the lithium ion battery that negative electrode material is composite transition metal oxide.In electricity
Under the conditions of current density 100mAh/g, constant current charge-discharge test is carried out within the scope of 0.02~3V of voltage, as voltage is down to 0.02V,
The first discharge specific capacity of battery is 733.6mAh/g, and initial charge specific capacity is 498.7mAh/g, 150 charge and discharge cycles
Afterwards, the specific capacity of the electrode material is 475.5mAh/g.
Claims (6)
1. a kind of method using stainless steel acid-washing waste liquid preparation carbon coating composite oxide powder, it is characterised in that: the side
Method includes following processing steps:
Step 1, the pH value of stainless steel acid-washing waste liquid is adjusted to 7~11 using solid base or aqueous slkali, mixes them thoroughly and gives birth to
At the mixed liquor containing sediment；
Step 2,1 gained mixed liquor of filtration step, and, in 400~700 DEG C of ball millings, combined oxidation will be obtained after gained sediment drying
Powder；
Step 3, dry after step 2 gained composite oxide powder being mixed with carbon source material, under argon atmosphere, 300~400 DEG C
Ball milling reacts 0.5~4h, obtains carbon coating composite oxide powder.
2. according to the method described in claim 1, it is characterized by: gained sediment drying is placed on ball in the step 2
In grinding machine, in 400~700 DEG C of 0.5~6h of ball milling, ball mill ratio of grinding media to material 10:1~20:1,60~80rpm of drum's speed of rotation.
3. according to the method described in claim 1, it is characterized by: the carbon source material is glucose, sugarcane in the step 3
Sugar, citric acid, malic acid, ethyl alcohol or Aqueous Solutions of Polyethylene Glycol or graphene powder.
4. according to the method described in claim 3, it is characterized by: in the step 3,
It, will be obtained by step 2 when carbon source material is glucose, sucrose, citric acid, malic acid, ethyl alcohol or Aqueous Solutions of Polyethylene Glycol
Composite oxide powder is dry after mixing with carbon source material, and under argon atmosphere, gained powder is placed in ball mill, in 300~
400 DEG C of 0.5~4h of ball milling, ball mill ratio of grinding media to material 10:1~20:1,60~80rpm of drum's speed of rotation；
When carbon source material is graphene powder, under argon atmosphere, institute after graphene powder is mixed with composite oxide powder
It obtains powder to be placed in ball mill, 0.5~4h of ball milling at room temperature~150 DEG C, ball mill ratio of grinding media to material 10:1~20:1, ball mill turn
60~80rpm of speed.
5. according to the method described in claim 1, it is characterized by: containing sediment obtained by filtration step 1 in the step 2
Mixed liquor obtain alkaline filtrate, obtained alkaline filtrate is neutralized, residual heavy metal ionic adsorption processing after meet it is useless
It is discharged after the standard of gurry discharge.
6. carbon coating composite oxide powder is as negative electrode of lithium ion battery made from any one of Claims 1 to 4 the method
The application of material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910430458.3A CN110078180A (en) | 2019-05-22 | 2019-05-22 | A method of carbon coating composite oxide powder is prepared using stainless steel acid-washing waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910430458.3A CN110078180A (en) | 2019-05-22 | 2019-05-22 | A method of carbon coating composite oxide powder is prepared using stainless steel acid-washing waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110078180A true CN110078180A (en) | 2019-08-02 |
Family
ID=67421299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910430458.3A Pending CN110078180A (en) | 2019-05-22 | 2019-05-22 | A method of carbon coating composite oxide powder is prepared using stainless steel acid-washing waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110078180A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112289991A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Ni and Cr co-doped carbon-coated lithium iron phosphate and preparation method and application thereof |
| CN115745006A (en) * | 2022-10-19 | 2023-03-07 | 景德镇陶瓷大学 | Low-temperature carbon coating method for amorphous oxide and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569726A (en) * | 2010-12-30 | 2012-07-11 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material coated with metal ions |
| CN103456932A (en) * | 2012-05-27 | 2013-12-18 | 湖南省正源储能材料与器件研究所 | Preparation method of energy storage material |
| CN103606654A (en) * | 2012-12-21 | 2014-02-26 | 燕山大学 | Method for preparing carbon-coated manganite composite material |
| JP2016500330A (en) * | 2012-12-03 | 2016-01-12 | アウディ アクチェンゲゼルシャフトＡｕｄｉ Ａｇ | Core-shell catalyst and method for palladium-based core particles |
| CN109346711A (en) * | 2018-11-27 | 2019-02-15 | 东北大学 | A kind of carbon coating lithium titanate, the preparation method and application of thulium doping |
| CN109546126A (en) * | 2018-11-27 | 2019-03-29 | 东北大学 | A kind of transition metal element doped carbon coating lithium titanate, preparation method and application |
-
2019
- 2019-05-22 CN CN201910430458.3A patent/CN110078180A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102569726A (en) * | 2010-12-30 | 2012-07-11 | 中国电子科技集团公司第十八研究所 | Method for preparing lithium ion battery anode material coated with metal ions |
| CN103456932A (en) * | 2012-05-27 | 2013-12-18 | 湖南省正源储能材料与器件研究所 | Preparation method of energy storage material |
| JP2016500330A (en) * | 2012-12-03 | 2016-01-12 | アウディ アクチェンゲゼルシャフトＡｕｄｉ Ａｇ | Core-shell catalyst and method for palladium-based core particles |
| CN103606654A (en) * | 2012-12-21 | 2014-02-26 | 燕山大学 | Method for preparing carbon-coated manganite composite material |
| CN109346711A (en) * | 2018-11-27 | 2019-02-15 | 东北大学 | A kind of carbon coating lithium titanate, the preparation method and application of thulium doping |
| CN109546126A (en) * | 2018-11-27 | 2019-03-29 | 东北大学 | A kind of transition metal element doped carbon coating lithium titanate, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| HUAN LIU等: "High-performance α-Fe2O3/C composite anodes for lithium-ion batteries synthesized by hydrothermal carbonization glucose method used pickled iron oxide red as raw material", 《COMPOSITES PART B:ENGINEERING》 * |
| 李小明 等: "不锈钢酸洗废液的处理与回收技术综述", 《化工环保》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112289991A (en) * | 2020-10-20 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Ni and Cr co-doped carbon-coated lithium iron phosphate and preparation method and application thereof |
| CN115745006A (en) * | 2022-10-19 | 2023-03-07 | 景德镇陶瓷大学 | Low-temperature carbon coating method for amorphous oxide and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Innovative application of acid leaching to regenerate Li (Ni1/3Co1/3Mn1/3) O2 cathodes from spent lithium-ion batteries | |
| CN108400399B (en) | Method for preparing lithium manganese phosphate/carbon cathode material from waste lithium manganate battery | |
| CN104953199B (en) | Metal-doped nickle cobalt lithium manganate using lithium ion cell anode waste synthesis and its production and use | |
| CN106622116B (en) | A kind of preparation method of spinel-type lithium-ion sieve | |
| CN105870438B (en) | A kind of lithium secondary battery lithium-rich anode composite material and preparation method | |
| CN103066280A (en) | Spherical lithium iron phosphate anode material and preparation method thereof | |
| Zhao et al. | Recycling technology and principle of spent lithium-ion battery | |
| CN102751549A (en) | Full-component resource reclamation method for waste positive electrode materials of lithium ion batteries | |
| CN102005563A (en) | Lithium ion battery high-voltage anode material preparation and surface coating method | |
| CN101488584A (en) | Asymmetric lithium iron phosphate cell using lithium titanate as main active substance of negative pole | |
| CN106784726B (en) | Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof | |
| CN110098441B (en) | Method for repairing and regenerating lithium cobaltate cathode material in waste battery | |
| CN106486657B (en) | Surface in-situ coated lithium-rich material and preparation method thereof | |
| CN106981651A (en) | Rubidium and/or the tertiary cathode material and preparation method, lithium ion battery of caesium doping | |
| CN106602024A (en) | In-situ surface-modified lithium-rich material and preparation method thereof | |
| CN112267023B (en) | Two-stage defluorination method for fluorine-containing material | |
| CN113072052A (en) | Waste lithium iron phosphate lithium supplement repair method and application | |
| CN102881873A (en) | Layered lithium-rich material preparation method | |
| CN112186287A (en) | Ball-milling spray regeneration method for waste lithium ion battery anode material | |
| WO2023155544A1 (en) | Preparation method for polyanionic positive electrode material | |
| CN101081695A (en) | Preparation method of doped modified ferric phosphate lithium | |
| CN110078180A (en) | A method of carbon coating composite oxide powder is prepared using stainless steel acid-washing waste liquid | |
| CN109678213A (en) | A kind of recycling and reuse method of lithium-ion battery lithium iron phosphate waste material | |
| CN106803588B (en) | A kind of recycling and reusing method of sodium sulfate waste liquid | |
| CN104218239B (en) | Preparation method for lithium nickel-cobalt manganate cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190802 |