CN104157872A - Low-cost high-capacity multiple-type nickel-manganese precursor, preparation method thereof and cathode material - Google Patents
Low-cost high-capacity multiple-type nickel-manganese precursor, preparation method thereof and cathode material Download PDFInfo
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- CN104157872A CN104157872A CN201410424231.5A CN201410424231A CN104157872A CN 104157872 A CN104157872 A CN 104157872A CN 201410424231 A CN201410424231 A CN 201410424231A CN 104157872 A CN104157872 A CN 104157872A
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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
- 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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a preparation method of a low-cost high-capacity multiply-type nickel-manganese precursor. The method includes following steps: (1) preparing a first solution to enable a mixed total concentration of nickel ion and manganese ion to be 0.5-1 mol/L, the content of a complexing agent to be 1.0-5.0 g/L, wherein a concentration ratio of the nickel ion and the manganese ion is Ni:Mn=0.5-0.9:0.1-0.5; (2) preparing a second solution which contains 2.0-10.0 mol/L of sodium hydroxide; and (3) feeding the first solution and the second solution into a reaction kettle in a co-current flow manner with a flow rate of the first solution being controlled to be 100-250 L/h, a reaction temperature being controlled to be 25-40 DEG C, a pH being controlled to range from 9.00 to 12.00 and a stirring rotary speed being controlled to be 200-400 rpm, performing a constant-temperature aging process in an aging kettle for 8-24 hours, performing a washing process and performing a drying process at 100-200 DEG C to obtain the low-cost high-capacity multiple-type nickel-manganese precursor. The invention provides the preparation method of the low-cost high-capacity multiple-type nickel-manganese precursor. By means of the method, a production cost is greatly reduced. In addition, compared with a material prepared through a conventional technology, a cathode material prepared from the precursor is significantly improved in electrical performances.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly a kind of preparation method of low cost high power capacity rate nickel manganese presoma.
Background technology
It is high that lithium ion battery has voltage, and specific capacitance is large, advantages such as safety, environmental protection and getting more and more people's extensive concerning.And lithium ion battery is mainly made up of positive electrode, negative material and electrolyte three parts, wherein positive electrode plays a part most critical to promoting lithium ion battery combination property.
In existing market positive electrode, cobalt acid lithium, nickle cobalt lithium manganate and LiMn2O4 occupy leading share substantially, wherein fluoric acid lithium is to drop into the earliest the anode material for lithium-ion batteries of commercially producing, but due to the factor that is subject to cobalt acid lithium high cost and environment is damaged, replaced gradually (comprising nickel-cobalt-manganese ternary material and the multicomponent material taking nickel cobalt manganese as other metallic elements of main body) by other Olivine-type Cathode Material in Li-ion Batteries; But this positive electrode difficulty of processing is large, and still can be to environment.
Ternary system conventional in lithium ion battery industry is disclosed in prior art patent of invention CN201210525623.1 " precursor of lithium ionic cell positive material and preparation method thereof " and CN201210525623.1 " preparation method of nickel-cobalt-manganese multi precursor of lithium ionic cell positive material ", and because cobalt price is high, be therefore necessary to research and develop a kind of nickel manganese binary positive electrode of removing cobalt element and replace nickel-cobalt-manganese ternary material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of low cost high power capacity rate nickel manganese presoma, and the preparation method of this presoma is provided.The inventive method is a kind of preparation technology of nickel manganese binary lithium ion anode material presoma, and the method has been optimized the technique in traditional mode of production binary or polynary lithium ion anode material presoma, has reduced widely production cost; And the material electrical property that the positive electrode electrical property preparing with presoma of the present invention is produced than traditional handicraft is also greatly improved.
The present invention solves the problems of the technologies described above adopted technical scheme: the preparation method of low cost high power capacity rate nickel manganese presoma, the chemical formula of described nickel manganese presoma is Ni
xmn
1-x(OH)
2, and 0.5<x<0.9 wherein; Said method comprising the steps of:
Step 1, is used nickel source, manganese source and complexing agent to prepare the first solution, and making the nickeliferous manganese ion of described the first solution mix total concentration is that 0.5～1mol/L, complexing agent content are 1.0-5.0g/L; Wherein nickel manganese ion concentration ratio is: Ni:Mn=0.5～0.9:0.1～0.5; Described complexing agent is selected from a kind of in L-Histidine, iminodiacetic acid or two kinds;
Step 2, preparation the second solution, described the second solution is the sodium hydroxide solution containing 2.0-10.0mol/L;
Step 3, by the first solution and the second solution and circulate into reactor, controlling the first liquid inventory is 100-250L/h, and reaction temperature is 25～40 DEG C, and pH scope is between 9.00-12.00, and speed of agitator is 200-400rpm; In course of reaction, the strict reaction process parameter of controlling, has reacted and has entered the ageing of aging reactor constant temperature after 8-24 hour, then washed, and dried under 100-200 DEG C of condition, obtains low cost high power capacity rate nickel manganese presoma Ni of the present invention
xmn
1-x(OH)
2.
Further, the nickel source of described the first solution is selected from nickelous sulfate or nickel chloride, and manganese source is selected from manganese sulfate or manganese chloride.
The low cost high power capacity rate nickel manganese presoma that adopts said method to prepare is granularity D50=3.0～4.0um, tap density >=1.40g/ml, the presoma of pattern rule.
Use above-mentioned presoma Ni
xmn
1-x(OH)
2prepare the method for anode material of lithium battery, further comprising the steps of: step 4, by described nickel manganese presoma Ni
xmn
1-x(OH)
2according to element mol ratio (Ni+Mn): Li=1:1.07-1.1 joins lithium, enters high temperature furnace and calcines after 6-12 hour at 500-900 DEG C, obtains described anode material of lithium battery LiNixMn
1-xo
2.
Further, described in, joining lithium refers to described nickel manganese presoma Ni
xmn
1-x(OH)
2mix with lithium source, described lithium source is the mixing of lithium carbonate or lithium hydroxide or two kinds of materials.
Compared with prior art, the present invention has following beneficial effect:
(1) prepare binary in industrial production now or ternary lithium ion anode material presoma mostly uses ammoniacal liquor as complexing agent; But along with social development proposes higher requirement to corporate environment, ammonia the pollution problem of production environment and water body is all subject to extensive concern all the time, herein using free of contamination organic substance as complexing agent, thoroughly solved this problem.
(2) well-known, in three kinds of metallic elements of nickel cobalt manganese, the price of cobalt is the highest, is a kind of nickel manganese binary presoma Ni and prepared by the present invention
xmn
1-x(OH)
2, (wherein 0.5<x<0.9), containing cobalt element, do not reduced cost significantly.
(3) the present invention mixes the presoma obtaining (lithium salts is lithium carbonate or lithium hydroxide or both compounding substances) and, 500-900 DEG C of calcining, obtains anode material of lithium battery (LiNi with lithium salts
xmn
1-xo
2), this material is assembled into and is tested after battery more than gram volume reaches 170mAh, more conventional ternary material gram volume 165mAh improves 5mAh.
(4) presoma granularity D50=3.0～4.0um that the present invention obtains, less than conventional ternary material D50=9.0～20.0um, therefore both can prepare positive electrode as presoma separately, also can use with conventional ternary material blending.
(5) the present invention strictly controls the first liquid inventory, reaction temperature, and the technological parameters such as speed of agitator, pH scope, are suitable for suitability for industrialized production.
Brief description of the drawings
Fig. 1 is Ni in embodiment 1
0.65mn
0.35(OH)
2the microcosmic Electronic Speculum figure of presoma.
Fig. 2 is Ni in embodiment 2
0.70mn
0.30(OH)
2the microcosmic Electronic Speculum figure of presoma.
Embodiment
In order to make goal of the invention of the present invention, technical scheme and useful technique effect more clear, below by embodiment, method of the present invention is described in further detail, but this is not limitation of the present invention, those skilled in the art are according to basic thought of the present invention, can make various amendments or improvement, all within the scope of the present invention.
Embodiment 1
With the nickel manganese hybrid ionic total concentration of crystalline sulfuric acid nickel and crystalline sulfuric acid manganese preparation Ni:Mn=0.65:0.35 be 0.8mol/L, complexing agent is using the iminodiacetic acid of 1.5g/L as the first solution; Naoh concentration is 8.0mol/L, as the second solution.By the first solution and the second solution simultaneously and circulate into reactor, controlling the first liquid inventory is 100L/h, and it is 35 DEG C that reaction temperature is set, and speed of agitator is 300rpm, strictly controls pH scope between 11.70-11.80; Reaction connects to be carried out, and feed liquid overflow entered aging reactor ageing after 8 hours, dried by its washing and at 150 DEG C, obtained D10=1.99, D50=3.69, and D90=6.88, tap density is 1.42g/ml, pattern Ni as shown in Figure 1
0.65mn
0.35(OH)
2presoma.This Ni.
0.65mn
0.35(OH)
2presoma particle diameter D50:3.69 micron, porosity is high, and BET is at 28.5m
2/ g, distributes and concentrates (D75-D25)/(D75+D25)=0.30.
By the presoma obtaining according to element mol ratio (Ni+Mn): after Li=1:1.09 mixes in Muffle furnace the heating rate with 3 DEG C/min, being raised to 750 DEG C calcines 10 hours, after cooling, pulverized and sieved, be assembled into battery, test battery gram volume reaches 171mAh again.
Embodiment 2
With the nickel manganese hybrid ionic concentration of crystallization nickel chloride and crystallization manganese chloride preparation Ni:Mn=0.70:0.30 be 0.7mol/L, complexing agent is using the L-Histidine of 2.5g/L as the first solution; Naoh concentration is 5.0mol/L, as the second solution, by the first solution and the second solution simultaneously and circulate into reactor, controlling the first liquid inventory is 250L/h, it is 40 DEG C that reaction temperature is set, and speed of agitator is 260rpm, strictly controls pH scope between 11.55-11.65; Reaction connects to be carried out, and feed liquid overflow entered aging reactor ageing after 10 hours, and it,, washing and drying at 150 DEG C, is obtained to D10=2.25, D50=3.75, D90=7.04, the Ni that tap density is 1.45g/ml
0.70mn
0.30(OH)
2presoma (Fig. 2).This Ni
0.70mn
0.30(OH)
2presoma particle diameter D50:3.75 micron, porosity is high, and BET is at 27.5m
2/ g, distributes and concentrates (D75-D25)/(D75+D25)=0.31.
By the presoma obtaining according to element mol ratio (Ni+Mn): after Li=1:1.09 mixes in Muffle furnace the heating rate with 3 DEG C/min, being raised to 800 DEG C calcines 8 hours, after cooling, pulverized and sieved, it is assembled into battery again, and test battery gram volume reaches 170mAh.
As mentioned above, just can realize preferably the present invention.
Claims (7)
1. the preparation method of low cost high power capacity rate nickel manganese presoma, is characterized in that, the chemical formula of described nickel manganese presoma is Ni
xmn
1-x(OH)
2, and 0.5<x<0.9 wherein; Said method comprising the steps of:
Step 1, is used nickel source, manganese source and complexing agent to prepare the first solution, and making the nickeliferous manganese ion of described the first solution mix total concentration is that 0.5～1mol/L, complexing agent content are 1.0-5.0g/L; Wherein nickel manganese ion concentration ratio is: Ni:Mn=0.5～0.9:0.1～0.5; Described complexing agent is selected from a kind of in L-Histidine, iminodiacetic acid or two kinds;
Step 2, preparation the second solution, described the second solution is the sodium hydroxide solution containing 2.0-10.0mol/L;
Step 3, by the first solution and the second solution and circulate into reactor, controlling the first liquid inventory is 100-250L/h, and reaction temperature is 25～40 DEG C, and pH scope is between 9.00-12.00, and speed of agitator is 200-400rpm; In course of reaction, the strict reaction process parameter of controlling, has reacted and has entered the ageing of aging reactor constant temperature after 8-24 hour, then washed, and dried under 100-200 DEG C of condition, obtains low cost high power capacity rate nickel manganese presoma Ni of the present invention
xmn
1-x(OH)
2.
2. the preparation method of low cost high power capacity rate nickel manganese presoma as claimed in claim 1, is characterized in that, the nickel source of described the first solution is selected from nickelous sulfate or nickel chloride, and manganese source is selected from manganese sulfate or manganese chloride.
3. low cost high power capacity rate nickel manganese presoma, is characterized in that, adopts method described in claim 1 or 2 to be prepared from.
4. low cost high power capacity rate nickel manganese presoma as claimed in claim 3, is characterized in that, described nickel manganese presoma is granularity D50=3.0～4.0um, tap density >=1.40g/ml, the presoma of pattern rule.
5. the preparation method of anode material of lithium battery, is characterized in that, makes the prepared nickel manganese presoma Ni of claim 1 or 2
xmn
1-x(OH)
2carry out following steps:
Step 4, by described nickel manganese presoma Ni
xmn
1-x(OH)
2according to element mol ratio (Ni+Mn): Li=1:1.07-1.1 joins lithium, enters high temperature furnace and calcines after 6-12 hour at 500-900 DEG C, obtains described anode material of lithium battery LiNixMn
1-xo
2.
6. the preparation method of anode material of lithium battery as claimed in claim 5, is characterized in that, described in join lithium and refer to described nickel manganese presoma Ni
xmn
1-x(OH)
2mix with lithium source, described lithium source is the mixing of lithium carbonate or lithium hydroxide or two kinds of materials.
7. anode material of lithium battery, is characterized in that, adopts the preparation method described in claim 5 or 6 to be prepared from.
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830631A (en) * | 2019-02-27 | 2019-05-31 | 深圳鸿鹏新能源科技有限公司 | Ceramic diaphragm and preparation method thereof and lithium ion battery |
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| CN101483238A (en) * | 2009-02-04 | 2009-07-15 | 宁波金和新材料有限公司 | Method of preparing lithium ionic positive pole material by using amino acid type organic as complexing agent |
| CN103715409A (en) * | 2012-09-29 | 2014-04-09 | 河南科隆集团有限公司 | Method for preparing coated lithium ion battery cathode material of lithium nickel manganese oxide |
-
2014
- 2014-08-26 CN CN201410424231.5A patent/CN104157872A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006104367A2 (en) * | 2005-04-01 | 2006-10-05 | Sk Energy Co., Ltd. | Layered core-shell cathode active materials for lithium secondary batteries, method for preparing thereof and lithium secondary batteries using the same |
| CN1870330A (en) * | 2005-05-27 | 2006-11-29 | 深圳市比克电池有限公司 | Multicomponent oxide containing cobalt nickel and preparation and application thereof |
| CN101483238A (en) * | 2009-02-04 | 2009-07-15 | 宁波金和新材料有限公司 | Method of preparing lithium ionic positive pole material by using amino acid type organic as complexing agent |
| CN103715409A (en) * | 2012-09-29 | 2014-04-09 | 河南科隆集团有限公司 | Method for preparing coated lithium ion battery cathode material of lithium nickel manganese oxide |
Non-Patent Citations (1)
| Title |
|---|
| YANG-KOOK SUN等: "Cobalt-Free Nickel Rich Layered Oxide Cathodes for Lithium-Ion Batteries", 《APPL. MATER. INTERFACES》, vol. 5, 15 October 2013 (2013-10-15) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109830631A (en) * | 2019-02-27 | 2019-05-31 | 深圳鸿鹏新能源科技有限公司 | Ceramic diaphragm and preparation method thereof and lithium ion battery |
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Application publication date: 20141119 |
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