CN104743536B - Preparation method of phosphate anode material - Google Patents
Preparation method of phosphate anode material Download PDFInfo
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- CN104743536B CN104743536B CN201510070980.7A CN201510070980A CN104743536B CN 104743536 B CN104743536 B CN 104743536B CN 201510070980 A CN201510070980 A CN 201510070980A CN 104743536 B CN104743536 B CN 104743536B
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Abstract
The invention relates to the technical field of lithium ion batteries and provides a preparation method of a phosphate anode material, in order to solve the problem that product property is reduced and unstable since impurity elements are introduced during raw material solid phase method synthesis and resistance is relatively large in the dynamical process of doping reaction. The preparation method comprises the following steps: (1) carrying out mixed ball milling on a phosphate and a precursor for 2-8 hours to obtain a mixture; (2) pre-sintering the mixture in inert gas at 300-450 DEG C for 2-12h, thus obtaining a pre-sintered product; (3) carrying out mixed ball milling on the pre-sintered product, a lithium source and a carbon source for 2-8h; (4) sintering the product obtained after ball milling in the step (3) in inert gas at 500-900 DEG C for 4-24h, thus obtaining a sintering product; and (5) fine crushing the sintered product and sieving to obtain the phosphate anode material. With adoption of the preparation method disclosed by the invention, the discharge performance of the product is improved effectively and the homogeneity and stability of the product are also enhanced.
Description
Technical field
The present invention relates to technical field of lithium ion, relate in particular to a kind of preparation side of phosphate-based positive electrode
Method.
Background technology
Lithium ion battery is mainly made up of positive electrode, negative material, electrolyte, diaphragm material four part, and positive pole material
The performance of material directly decides the performance of lithium ion battery.Phosphate-based positive electrode has high security performance and circulation longevity
Life, and have the advantages that simultaneously nontoxic, pollution-free, raw material sources extensively, low price, be the reason of lithium ion battery of new generation
Think positive electrode.But the electronic conductance of phosphate-based positive electrode itself, ionic conductance are all very low, are not suitable for filling of high current
Electric discharge is so as to be obstructed in application aspect.Theory and practice are all it has been proved that the doping of the element such as nb, zr, ti, mg, al can have
Effect improves the charge-discharge performance of phosphate-based positive electrode.It is generally all with the oxide of doping metals, carbon in Solid phase synthesis
Hydrochlorate, sulfate, nitrate, oxalates, acetate, chloride, hydroxide etc. are as doped compound.But the sulfur being introduced into
Acid group, nitrate anion and chloride ion etc. belong to impurity element, need to remove in sintering, its catabolite poisonous and harmful, and difficult
To decompose completely.They are all larger with phosphatic crystal structure diversity ratio simultaneously, and the dynamic process resistance ratios of doping are larger,
It is easily caused doping uneven, so component segregation and failure, cause properties of product to reduce, product stability is poor, and this is also mesh
The greatest difficulty facing of front phosphate cathode material.
The Chinese patent of Application No. 201110267354.9 discloses a kind of anode material for lithium-ion batteries magnesium metal and mixes
Miscellaneous lithium manganese phosphate/carbon preparation method, this patent comprises the following steps: (1) presoma preparation: take lithium source, phosphorus source, manganese source, magnesium
Source and carbon-source cpd, ball mill mixing is to uniform；(2) ball mill pulverizing presoma: the mixture that step (1) is obtained is dried, ball
Wear into microgranule；(3) calcination process: mixture is calcined 1～12h under 500～800 DEG C of inert atmospheres, obtains carbon coating magnesium and mix
Miscellaneous lithium manganese phosphate granule.Its doped compound used is magnesium nitrate, magnesium sulfate, magnesium chloride, magnesium acetate, magnesium oxide.Wherein
Magnesium nitrate, magnesium sulfate, magnesium chloride introduce nitrogen, sulfur, chlora prime element respectively, and can resolve into titanium dioxide during its high temperature sintering
The poisonous and hazardous gas such as nitrogen, sulfur dioxide, chlorine, and be not easily decomposed cause completely material property reduce.And magnesium oxide then by
Big in doping reaction resistance, frequently result in the uneven situation of doping and occur.
The Chinese patent of Application No. 201010142529.9 discloses a kind of multielement-doped lithium iron phosphate positive electrode material
And preparation method thereof, which disclose a kind of multielement-doped lithium iron phosphate positive electrode material, its composition formula is: li1-
xaxfe1-y-znbymzpo4；The Chinese patent of Application No. 200810071494.7 discloses a kind of conducting phosphide-doped
The preparation method of lithium iron phosphate cathode material, lithium salts, ferrous salt, reducing agent are uniformly mixed by this invention, remix wet grinding and are situated between
Matter, adds ortho phosphorous acid or sodium hypophosphite, phosphate, carbon compound and carbon dust, ball milling 3～15 hours, 50 DEG C～105
Normal pressure or vacuum drying at a temperature of DEG C；The powder body being dried is placed in inert atmosphere or weakly reducing atmosphere, using double sintering
Method prepares conducting phosphide-doped lithium iron phosphate cathode material.All there is same, i.e. introducing impurity element in them,
Produce poisonous and harmful by-product, simultaneous reactions energy resistance is big, and uniform doping is difficult to ensure that.
Content of the invention
It is larger in order to solve introducing impurity element and doping reaction dynamic process resistance ratios in material Solid phase synthesis,
Properties of product are led to reduce and unstable problem, the present invention proposes a kind of preparation method of phosphate-based positive electrode, energy
Effectively improve the discharge performance of product, simultaneously the stability of improving product.
The present invention is achieved by the following technical solutions: a kind of preparation method of phosphate-based positive electrode, described
Preparation method is:
(1) by phosphate and presoma mixing and ball milling 2～8 hours, obtain mixture；
Preferably, phosphate is 0.01～0.2: 1 with the mol ratio of presoma.Described phosphate is selected from nb3
(po4)5, zr3(po4)4, ti3(po4)4, mg3(po4)2, alpo4One or more of.Described presoma is selected from mpo4Or
m3(po4)2, wherein m is selected from one of fe, mn, ni, co.
(2) mixture is placed in noble gases in 300 DEG C～450 DEG C presintering 2～12 hours, obtains presintering and produce
Thing；
(3) by presintering product and lithium source, carbon source mixing and ball milling 2～8 hours；
Preferably, presintering product is 1: 0.95～1.05 with the mol ratio of lithium source, carbon source addition produces for presintering
The 3%～15% of amount of substance.Described lithium source is selected from one or more of lithium carbonate, Lithium hydrate, lithium acetate, lithium oxalate.
Described carbon source is selected from one or more of glucose, sucrose, superconduction white carbon black, Graphene, CNT.
Add lithium source that lithium ion can be made to be diffused in presoma after presintering, form reasonable lithium ion diffusion logical
Road, is conducive to the charge-discharge performance of battery.
(4) product after step (3) ball milling is placed in noble gases and sinters 4～24 hours at 500 DEG C～900 DEG C, obtain
To sintered product；
(5) sintered product obtains a kind of phosphate-based positive electrode after in small, broken bits sieving.
Preferably, above-mentioned noble gases are selected from nitrogen or argon.
The present invention is directly doped to phosphate cathode material using the phosphate of doped metallic elements, can not in addition draw
Enter impurity element, effectively reduce reaction resistance so that uniform doping is consistent simultaneously.
Compared with prior art, the invention has the beneficial effects as follows: effectively improve the discharge performance of product, simultaneously improving product
Concordance and stability.
Brief description
Fig. 1 is the discharge curve of the lithium ion battery with embodiment 1 as positive electrode；
Fig. 2 is the transmission electron microscope picture with embodiment 1 as positive electrode.
Specific embodiment
Below by embodiment and accompanying drawing, the present invention is described in further detail.
Embodiment 1
(1) by mg3(po4)2With mnpo4Presoma in molar ratio 0.1: 1, mixing and ball milling 5 hours, obtain mixture；
(2) mixture is placed in nitrogen in 400 DEG C of presintering 7 hours, obtains presintering product；
(3) by presintering product and lithium carbonate, Graphene mixing and ball milling ball milling 5 hours, wherein, presintering product and carbonic acid
The mol ratio of lithium is 1: 1, and the addition of Graphene is the 10% of presintering product quality；
(4) product after step (3) ball milling is sintered 14 hours at 500 DEG C in nitrogen, obtain sintered product；
(5) sintered product obtains mg-doped limnpo after in small, broken bits sieving4Positive electrode.
The doping limnpo being obtained with embodiment 14Positive electrode is that the discharge curve of lithium ion battery is as shown in Figure 1；Just
The transmission electron microscope picture of pole material is as shown in Figure 2.
Embodiment 2
(1) by nb3(po4)5With fepo4Presoma in molar ratio 0.01: 1, mixing and ball milling 2 hours, obtain mixture；
(2) mixture is placed in argon in 300 DEG C of presintering 12 hours, obtains presintering product；
(3) by presintering product and Lithium hydrate, glucose, sucrose mixing and ball milling ball milling 8 hours, wherein, presintering is produced
Thing is 1: 0.95 with the mol ratio of Lithium hydrate, and glucose is the 3% of presintering product quality with the addition of sucrose, wherein,
Glucose is 1: 1 with the mass ratio of sucrose；
(4) product after step (3) ball milling is sintered 24 hours at 700 DEG C in argon, obtain sintered product；
(5) sintered product obtains niobium doping lif after in small, broken bits sievingepo4Positive electrode.
Embodiment 3
(1) by ti3(po4)4With copo4Presoma in molar ratio 0.05: 1, mixing and ball milling 8 hours, obtain mixture；
(2) mixture is placed in nitrogen in 450 DEG C of presintering 2 hours, obtains presintering product；
(3) by presintering product and lithium oxalate, superconduction white carbon black mixing and ball milling ball milling 2 hours, wherein, presintering product and grass
The mol ratio of sour lithium is 1: 1.05, and the addition of superconduction white carbon black is the 15% of presintering product quality；
(4) product after step (3) ball milling is sintered 4 hours at 900 DEG C in nitrogen, obtain sintered product；
(5) sintered product obtains titanium doped licopo after in small, broken bits sieving4Positive electrode.
Embodiment 4
(1) by ti3(po4)4, alpo4 and ni3(po4)2Presoma in molar ratio 0.1: 0.1: 1, mixing and ball milling 6 hours, obtain
To mixture；
(2) mixture is placed in nitrogen in 350 DEG C of presintering 10 hours, obtains presintering product；
(3) by presintering product and lithium carbonate, lithium acetate, CNT mixing and ball milling ball milling 5 hours, wherein, presintering
Product is 1: 0.55: 0.5 with the mol ratio of lithium carbonate, lithium acetate, and the addition of CNT is presintering product quality
7%；
(4) product after step (3) ball milling is sintered 18 hours at 600 DEG C in nitrogen, obtain sintered product；
(5) sintered product obtains aluminum titanium dual element doping linipo after in small, broken bits sieving4Positive electrode.
Embodiment 5
(1) by zr3(po4)4、mg3(po4)2, alpo4 and mnpo4Presoma in molar ratio 0.02: 0.05: 0.08: 1, mixes
Close ball milling 4 hours, obtain mixture；
(2) mixture is placed in nitrogen in 400 DEG C of presintering 5 hours, obtains presintering product；
(3) by presintering product and lithium carbonate, Graphene, glucose mixing and ball milling ball milling 4 hours, wherein, presintering is produced
Thing is 1: 0.98 with the mol ratio of lithium carbonate, and Graphene is the 12% of presintering product quality with the addition of glucose, wherein
Graphene is 2: 8 with the mass ratio of glucose；
(4) product after step (3) ball milling is sintered 8 hours at 800 DEG C in nitrogen, obtain sintered product；
(5) sintered product obtains zirconium magnalium multi-element doping limnpo after in small, broken bits sieving4Positive electrode.
The present invention effectively improves the discharge performance of product, and capacity multiplying power is all very outstanding, and one time average grain size is also little
In 200 nanometers, battery with two side terminals is got a promotion with stability simultaneously.
Claims (5)
1. a kind of preparation method of phosphate-based positive electrode is it is characterised in that described preparation method is:
(1) by phosphate and presoma mixing and ball milling 2 ~ 8 hours, obtain mixture；Described phosphate is selected from nb3(po4)5, zr3
(po4)4, ti3(po4)4, mg3(po4)2, alpo4One or more of；Described presoma is selected from mpo4Or m3(po4)2,
Wherein m is selected from one of fe, mn, ni, co；
(2) mixture is placed in noble gases in 300 DEG C～450 DEG C presintering 2 ~ 12 hours, obtains presintering product；
(3) by presintering product and lithium source, carbon source mixing and ball milling 2 ~ 8 hours；
(4) product after step (3) ball milling is placed in noble gases and sinters 4 ~ 24 hours at 500 DEG C～900 DEG C, sintered
Product；
(5) sintered product obtains a kind of phosphate-based positive electrode after in small, broken bits sieving.
2. a kind of preparation method of phosphate-based positive electrode according to claim 1 is it is characterised in that in step (1)
Phosphate is 0.01～0.2:1 with the mol ratio of presoma.
3. a kind of preparation method of phosphate-based positive electrode according to claim 1 is it is characterised in that in step (3)
Presintering product is 1:0.95～1.05 with the mol ratio of lithium source, and carbon source addition is the 3% ~ 15% of presintering product quality.
4. the preparation method of a kind of phosphate-based positive electrode according to claim 1 or 3 is it is characterised in that step (3)
Described in lithium source be selected from one or more of lithium carbonate, Lithium hydrate, lithium acetate, lithium oxalate.
5. the preparation method of a kind of phosphate-based positive electrode according to claim 1 or 3 is it is characterised in that step (3)
Described in carbon source be selected from one or more of glucose, sucrose, superconduction white carbon black, Graphene, CNT.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857215A (en) * | 2010-06-22 | 2010-10-13 | 中国人民解放军国防科学技术大学 | Preparation method of high tap density lithium iron phosphate (LiFePO4) |
| CN102237520A (en) * | 2010-04-23 | 2011-11-09 | 刘国奇 | Method for preparing high capacity lithium iron phosphate cathode material by double sintering |
| CN102623695A (en) * | 2012-03-29 | 2012-08-01 | 天津巴莫科技股份有限公司 | Phosphate lithium ion battery cathode material and preparation method thereof |
| CN104332628A (en) * | 2014-09-04 | 2015-02-04 | 北汽福田汽车股份有限公司 | Preparation method and lithium ion battery of lithium ion battery positive material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150140431A1 (en) * | 2012-04-05 | 2015-05-21 | Hitachi Metals, Ltd. | Method for producing positive electrode active material for nonaqueous secondary batteries, positive electrode for nonaqueous secondary batteries, and nonaqueous secondary battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102237520A (en) * | 2010-04-23 | 2011-11-09 | 刘国奇 | Method for preparing high capacity lithium iron phosphate cathode material by double sintering |
| CN101857215A (en) * | 2010-06-22 | 2010-10-13 | 中国人民解放军国防科学技术大学 | Preparation method of high tap density lithium iron phosphate (LiFePO4) |
| CN102623695A (en) * | 2012-03-29 | 2012-08-01 | 天津巴莫科技股份有限公司 | Phosphate lithium ion battery cathode material and preparation method thereof |
| CN104332628A (en) * | 2014-09-04 | 2015-02-04 | 北汽福田汽车股份有限公司 | Preparation method and lithium ion battery of lithium ion battery positive material |
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