CN100579899C - Method of producing lithium iron phosphate with high compacted density and excellent adhesive property - Google Patents
Method of producing lithium iron phosphate with high compacted density and excellent adhesive property Download PDFInfo
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- CN100579899C CN100579899C CN200710062543A CN200710062543A CN100579899C CN 100579899 C CN100579899 C CN 100579899C CN 200710062543 A CN200710062543 A CN 200710062543A CN 200710062543 A CN200710062543 A CN 200710062543A CN 100579899 C CN100579899 C CN 100579899C
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- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a preparing method for phosphate iron lithium with high compacted density and good cohesiveness. The technical points are as follows: firstly, ferric oxide, phosphate dihydrogen lithium, oxide or carbonate doping metal elements and carbon source are ball-milled evenly in aqueous solution and are then sprayed and dried so spherical powder is obtained; the spherical powder is secondly mixed with carbon source; after ball-milling and in nitrogen atmosphere protection, the mixture is presintered for 4 hours to 48 hours in 300 DEG C to 400 DEG C; after breaking, the mixture is heat treated for 4 hours to 48 hours in a high temperature of 600 DEG C to 800 DEG C so the phosphate iron lithium with high compacted density and good cohesiveness is obtained. The present invention has the advantages that the phosphate iron lithium prepared by the present invention is good in cohesiveness when used as lithium ion battery anode, an anode plate is high in compacted density, softness and winding performance. The preparing method generates no harmful gas, costs little, is simple in process and especially suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of high compacted density good cohesiveness method preparing phosphate iron lithium, be applicable to the prepared iron lithium phosphate of the present invention and do anode material for lithium-ion batteries.
Background technology
Lithium ion battery is since nineteen ninety comes out, advantages such as voltage height, energy density are big because it has, long service life, memory-less effect and operating temperature range are wide, popularize rapidly, be widely used in the portable equipments such as mobile phone, MP3, UPS, photographic camera, notebook computer.Heavy body, high-power lithium ion battery are at the early-stage in the first-class application of power tool, electric bicycle, electromobile, and application prospect is good.
Positive electrode material is the important component part of decision lithium ion battery performance.At present, the positive electrode material of large-scale commercial applications application is LiC
OO
2, LiMn
2O
4, LiC
O1/3Ni
1/3Mn
1/3O
2, LiC
OO
2Because contain cobalt amount height (about 60%), cobalt resource is in great shortage, costs an arm and a leg, and the application on high capacity cell is restricted; LiC
O1/3Ni
1/3Mn
1/3O
2The high rate performance of material is relatively poor, can not satisfy the requirement of power cell; LiMn
2O
4Cheap but its high temperature cyclic performance is poor, can shorten work-ing life of battery during frequent high power discharge greatly, and this material there is certain dissolubility in electrolytic solution, storge quality is poor.Therefore researching and developing novel anode material becomes present focus.
Lithium ion battery material iron lithium phosphate (LiFePO
4) be one of novel material of studying both at home and abroad at present, studies show that this material has the following advantages: cheap, raw material is easy to get, operating voltage is moderate, discharge is steady, and specific storage is higher, Stability Analysis of Structures, safety performance and cycle life are splendid, storge quality is excellent, and is environmentally friendly, is real green energy resource.
Chinese patent CN1581537A discloses " a kind of preparation method of lithium ion battery anode material lithium iron phosphate ", its technical essential is with metal iron powder, tertiary iron phosphate, Trilithium phosphate, doped element phosphoric acid salt, conductive agent or conductive agent presoma mix in proportion, said mixture is put into the ball mill container of filling argon gas or nitrogen atmosphere, ball milling 18-36 hour, the ball milling product places High Temperature Furnaces Heating Apparatus, in argon gas or nitrogen atmosphere, heat up with 10-30 ℃/min heating rate, in 450-750 ℃ of constant temperature calcining 10-60min, with 10-30 ℃/min cooling rate cool to room temperature, make iron phosphate powder or doped iron lithium phosphate powder then.
Above-mentioned preparation method's shortcoming is that the raw material composition is more, makes troubles to preparation, and in addition, its roasting number of times is for once, sufficient reacting degree shortcoming.
Summary of the invention
Technical problem to be solved by this invention provides the high compacted density good cohesiveness method preparing phosphate iron lithium that a kind of with low cost, technology is simple, be fit to suitability for industrialized production and environmental protection.
The present invention adopts following technical scheme:
High compacted density good cohesiveness method preparing phosphate iron lithium is characterized in that:
(1) take by weighing following each raw material by ratio of weight and the number of copies:
Monometallic: 100
Ferric oxide: 70-85
Carbon source: 5-25
The 5-95% of monometallic, ferric oxide and the carbon source total amount that takes by weighing in (2) earlier will above-mentioned (1) going on foot joins in the deionized water, the amount of deionized water is 1.5-6.5 a times of above-mentioned raw materials total amount, monometallic is water-soluble, other raw material is a solid phase, carried out solution and solid phase mix grinding then 4-48 hour, be dispersed in the solution until solid matter, obtaining solid content is the suspension slurry of 15-60%;
(3) with the spray-dried spherical solid phase powder of even-grained class that obtains of above-mentioned suspension slurry;
(4) add remaining carbon source in the spherical solid phase powder of above-mentioned class, promptly add the 95-5% that the carbon source amount is the carbon source total amount the 2nd time, the doping of twice carbon coats and makes the conductivity of material improve; Dry ball milling 0.5-48 hour, until obtaining homodisperse powder;
(5) with above-mentioned powder under nitrogen atmosphere protection, 300-400 ℃ carry out the 1st time the calcining, calcination time is 4-48 hour;
(6) will cross 200 mesh sieves then through material ball milling 4-48 hour after the 1st calcining;
(7) with behind the material briquetting after above-mentioned the sieving or directly under nitrogen atmosphere protection, carry out the 2nd calcining at 600-800 ℃, calcination time is 4-48 hour;
(8) material after above-mentioned the 2nd calcining is pulverized the back and cross 200 mesh sieves, get the iron lithium phosphate that carbon coats.
The present invention also adds the raw material of following weight parts: the oxide compound of doped metallic elements or carbonate: 0.05-5 in above-mentioned (1) step.
The present invention before solution and solid phase mix grinding, also adds oxide compound or carbonate by the doped metallic elements of ratio requirement in above-mentioned (2) step.
Carbon source of the present invention is selected from one or more in scale graphite, acetylene black, sucrose, the glucose; The carbon source that adds for the 1st time is selected from crystalline flake graphite or/and acetylene black; The carbon source that adds for the 2nd time is selected from sucrose or/and glucose.
Doped metallic elements of the present invention is selected from one or more in magnesium, aluminium, the zirconium.Mixing of metallic element improved the conductivity of material.
The LiFePO 4 material of the present invention's preparation, tap density can reach 1.2-1.7g/cm
3, lithium ion battery negative is in being during firm little carbon ball, when being assembled into 14500 circular batteries, and room temperature initial charge specific storage＞150mAh/g, first discharge specific capacity＞130mAh/g, compacts density＞2.35g/cm
3, the electrode slice softness has excellent coiling performance, is fit to large-scale industrial production.
Beneficial effect of the present invention is as follows:
(1) iron lithium phosphate with the present invention's preparation has high jolt ramming and compacted density, and tap density can reach 1.2-1.7g/cm
3And has high adhesive property.
When (2) iron lithium phosphate for preparing with the present invention was used as based lithium-ion battery positive plate, electrode slice had high compacted density, rolling anodal volume density＞2.35g/cm
3And the flexibility and the coiling of positive plate are good.
(3) higher with the lithium cell specific storage of the ferric phosphate positive pole material assembling of the present invention preparation, have extended cycle life.
(4) this preparation method does not have obnoxious flavour and produces, and helps environmental protection, and with low cost, technology is simple, is specially adapted to large-scale industrial production.
Description of drawings
Fig. 1 is the SEM figure of the prepared magniferous iron lithium phosphate of the embodiment of the invention 1.
Fig. 2 is the XRD figure of the prepared magniferous iron lithium phosphate of the embodiment of the invention 1.
Fig. 3 is the first charge-discharge curve of the embodiment of the invention 1.
Fig. 4 discharges and recharges life curve for 500 2.5-4.2V100%DOD of the embodiment of the invention 1.
Embodiment
Embodiment 1
The 2.5Kg deionized water is added in the ball grinder, add 500gLiH
2PO
4, 380.3gFe
2O
3, 1.92gMgO, 40g acetylene black and 20g crystalline flake graphite.Wet ball mill obtains uniform suspension slurry after 24 hours, the spray-dried spherical solid phase presoma 1 of class that obtains is got the mixing of 500g solid phase presoma 1 and 50g sucrose ball milling and obtained presoma 2 in 6 hours.Presoma 2 is at N
2Calcined the calcinate that obtains 24 hours through 350 ℃ under the atmosphere protection.Calcinate after 24 hours, is crossed 200 mesh sieves, again at N through ball mill crushing
2Through 720 ℃ of calcinings 24 hours, cross 200 mesh sieves and obtain magnesium doped iron lithium phosphate sample 1 under the atmosphere protection, its tap density is 1.26g/cm
3, compacts density 2.35g/cm
3The time electrode slice softness.Its SEM figure sees Fig. 1, be particle spherical particle uniformly as can be seen, XRD figure is seen Fig. 2, and as seen it is the pure phase iron lithium phosphate, and the first charge-discharge graphic representation is seen Fig. 3, see that 0.1C initial discharge specific storage is 150.8mAh/g and 131.4mAh/g, the 1C initial specific storage of discharging is 120.5mAh/g, and 500 2.5-4.2V100%DOD of 1C circulation discharge and recharge life curve and see Fig. 4, and as seen its cycle performance is good, 500 times capability retention is 97.8%, and capacitance loss has only 2.2%.
Embodiment 2
The 2.5Kg deionized water is added in the ball grinder, add 500gLiH
2PO
4, 384.3gFe
2O
3, 25g acetylene black and 20g crystalline flake graphite.Add ball mill behind the premix, ball milling 24 hours, spraying drying obtains solid phase presoma 1, gets solid phase presoma 500g and 40.0g sucrose, mixes broken 3 hours through ball milling, obtains presoma 2.Solid phase presoma 2 is at N
2Under the atmosphere protection, calcine the calcinate that obtained in 12 hours through 350 ℃.Calcinate is through ball mill crushing 24 hours, again at N
2Through 700 ℃ of calcinings 24 hours, cross 200 mesh sieves obtain the undoping iron lithium phosphate sample 2 of metallic element under the atmosphere protection, its tap density is 1.67g/cm
3, compacts density 2.46g/cm
3The time, electrode slice softness and cohesiveness are good.The initial charge/discharge specific storage is respectively 153.3mAh/g and 133.6mAh/g.
Embodiment 3-8 sees the following form:
Annotate:
(1) proportioning that goes up in the table is a ratio of weight and number.
(2) the concrete preparation method of embodiment 3-8 requires to do to obtain iron lithium phosphate according to the technical scheme of summary of the invention part.
(3) carbon source in the last table is selected from one or more in scale graphite, acetylene black, sucrose, the glucose; The carbon source that adds for the 1st time is selected from crystalline flake graphite or/and acetylene black; The carbon source that adds for the 2nd time is selected from sucrose or/and glucose.
(4) doped metallic elements in the last table is selected from one or more in magnesium, aluminium, the zirconium.
Claims (2)
1, high compacted density good cohesiveness method preparing phosphate iron lithium is characterized in that:
(1) take by weighing following each raw material by ratio of weight and the number of copies:
Monometallic: 100
Ferric oxide: 70-85
Carbon source: 5-25
The 5%-95% of monometallic, ferric oxide and the carbon source total amount that takes by weighing in (2) earlier will above-mentioned (1) going on foot joins in the deionized water, the amount of deionized water is 1.5-6.5 a times of above-mentioned raw materials total amount, carried out solution and solid phase mix grinding then 4-48 hour, be dispersed in the solution until solid matter, obtaining solid content is the suspension slurry of 15%-60%;
(3) with the spray-dried spherical solid phase powder of epigranular class that obtains of above-mentioned suspension slurry;
(4) in the spherical solid phase powder of above-mentioned class, add remaining carbon source, promptly add the 95%-5% that the carbon source amount is the carbon source total amount the 2nd time, dry ball milling 0.5-48 hour, until obtaining homodisperse powder;
(5) with above-mentioned powder under nitrogen atmosphere protection, carry out the 1st calcining at 300-400 ℃, calcination time is 4-48 hour;
(6) will cross 200 mesh sieves then through material ball milling 4-48 hour after the 1st calcining;
(7) with the material after above-mentioned the sieving directly under nitrogen atmosphere protection, carry out the 2nd calcining at 600-800 ℃, calcination time is 4-48 hour;
(8) material after above-mentioned the 2nd calcining is pulverized the back and cross 200 mesh sieves, get the iron lithium phosphate that carbon coats;
Described carbon source is selected from one or more in scale graphite, acetylene black, sucrose, the glucose; The carbon source that adds for the 1st time is selected from crystalline flake graphite or/and acetylene black; The carbon source that adds for the 2nd time is selected from sucrose or/and glucose.
2, high compacted density good cohesiveness method preparing phosphate iron lithium according to claim 1 is characterized in that also adding the raw material of following weight parts: the oxide compound of doped metallic elements or carbonate: 0.05-5 in above-mentioned (1) step;
In above-mentioned (2) step, before solution and solid phase mix grinding, also add oxide compound or carbonate by the doped metallic elements of ratio requirement;
Described doped metallic elements is selected from one or more in magnesium, aluminium, the zirconium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710062543A CN100579899C (en) | 2007-08-10 | 2007-08-10 | Method of producing lithium iron phosphate with high compacted density and excellent adhesive property |
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|---|---|---|---|
| CN200710062543A CN100579899C (en) | 2007-08-10 | 2007-08-10 | Method of producing lithium iron phosphate with high compacted density and excellent adhesive property |
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| CN100579899C true CN100579899C (en) | 2010-01-13 |
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| CN101330141B (en) * | 2008-07-18 | 2010-06-02 | 清华大学 | Method for preparing lithium ionic battery anode material spherical LiFePO4 /C |
| CN101640267B (en) * | 2009-07-30 | 2011-11-02 | 宁波英特维新材料有限公司 | Preparation method of lithium iron phosphate as cathode material of lithium ion battery |
| CN101714658B (en) * | 2009-11-05 | 2012-03-07 | 湖南维邦新能源有限公司 | Preparation method of lithium iron phosphate for lithium ion battery |
| CN101777645B (en) * | 2010-02-10 | 2012-08-22 | 赵县强能电源有限公司 | Preparation method of carbon-modified lithium titanate |
| DE102010021804A1 (en) * | 2010-05-27 | 2011-12-01 | Süd-Chemie AG | Composite material containing a mixed lithium metal phosphate |
| CN102185138B (en) * | 2011-01-28 | 2013-12-11 | 厦门钨业股份有限公司 | Preparation method of composite lithium iron phosphate material |
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| CN112768688B (en) * | 2019-11-05 | 2023-06-06 | 贝特瑞（天津）纳米材料制造有限公司 | Lithium iron phosphate material, preparation method thereof and lithium ion battery |
| CN115196611A (en) * | 2022-07-26 | 2022-10-18 | 江西赣锋锂电科技股份有限公司 | Low-cost lithium iron phosphate and preparation method of lithium manganese iron phosphate |
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