CN102623695A - Phosphate lithium ion battery cathode material and preparation method thereof - Google Patents
Phosphate lithium ion battery cathode material and preparation method thereof Download PDFInfo
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- CN102623695A CN102623695A CN2012100876774A CN201210087677A CN102623695A CN 102623695 A CN102623695 A CN 102623695A CN 2012100876774 A CN2012100876774 A CN 2012100876774A CN 201210087677 A CN201210087677 A CN 201210087677A CN 102623695 A CN102623695 A CN 102623695A
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Abstract
The invention discloses a phosphate lithium ion battery cathode material and a preparation method thereof. The method comprises the following steps: 1, preparing precursor; 2, placing obtained precipitation, lithium source, carbon source and solvent in a ball grinder in a designed ratio to mix 1-24 hour(s), wherein the molar ratio of metal to Li is 1:1-1.05, the carbon source is calculated as a product carbon content of 1-6 percent, and the solvent is calculated in the way that the quality ratio of liquid to solid is 1-20:1; 3, spraying and drying mixed slurry; and 4, placing dried material in a roasting furnace at the temperature of 500-900 DEG C for 4-24 hours under the protection of inert gas, so as to obtain the cathode material. The method provided by the invention solves the problems that a conventional phosphate lithium ion battery cathode material has low ionic electric conductivity and poor multiplying power performance, the product processability is good, the preparation technology is simple, and large-scale industrialization production is very feasible and has market prospect.
Description
Technical field
The present invention relates to the lithium ion secondary battery anode material field, particularly relate to a kind of phosphate-based positive electrode and preparation method thereof.
Background technology
In the face of human demands for energy is increased severely day by day, the primary energy reserves reduce gradually, and the development and application of novel energy becomes and solves one of feasible measure of energy problem.Compare with traditional cobalt acid lithium battery as the lithium ion battery of positive pole with phosphate-based material; Have the security performance height, have extended cycle life, performance advantage such as with low cost, environmental protection; Therefore by the industry extensive concern, it is representing the future thrust of power battery anode material.But the phosphate-based material high rate performance of pure phase is not good enough, becomes a key difficult problem that limits this series material large-scale application.
Phosphate-based material high rate performance difference causes owing to material electronics conductivity and lithium ion diffusion rate are all low.Research shows that the material electronics conductivity can coat through conductive agent and be significantly improved.And the improvement method of material lithium ion diffusion velocity is still existed various technical barriers at present; For example: think on the mechanism that element doping can be through modifying the passage that cell parameter enlarges lithium ion conduction; But doping techniques is difficult to grasp, to material to improve consistency relatively poor; The preparation nanometer materials have shortened the free path of lithium ion diffusion, can effectively improve diffusion velocity, but nanometer materials are harsh to the processing technology requirement of pole piece, and domestic enterprise does not grasp the core technology that nano material is processed into pole piece as yet.According to document to lithium ion the diffusion mechanism research in phosphate-based material can know that the diffusion of lithium ion only can belong to dimension diffusion along the diffusion of the b axle of olivine structural crystal, causes the high rate performance of material relatively poor.
Summary of the invention
The purpose of this invention is to provide the good LiMPO of a kind of high rate performance
4The preparation method of/C positive electrode.
The objective of the invention is to realize through following technical scheme:
The phosphate-based positive electrode of a kind of lithium ion battery, its structural group becomes LiMPO
4/ C, wherein M is a metallic element, carbon content is 1～6% (wt%).Wherein said metallic element M is Fe, Mn or Co.
The preparation method of the phosphate-based positive electrode of a kind of above-mentioned lithium ion battery may further comprise the steps:
1) preparation phosphate precursor: dispose metal salt solution and the 1mol/L phosphoric acid solution of 1mol/L respectively, metal salt solution is injected agitated reactor, open and stir; Add the fluorocarbon surfactant of liquor capacity 1%～5% metering, squeeze into phosphoric acid solution with the speed that is lower than 500ml/min, treat that phosphoric acid solution adds after; Adding ammoniacal liquor adjusting pH is 2～4, and reaction is carried out suction filtration, washing with material more than 6 hours then; Wash to washings pH be 8～9, the oven dry, obtain the phosphate precursor;
2) place ball mill to mix with lithium source, carbon source, solvent 1～24 hour according to design proportion gained phosphate precursor; Wherein the mol ratio of metal and lithium is M: Li=1: 1～1.05; Carbon source is 1%～6% calculating by the product carbon content, Gu solvent is 1～20: 1 calculating according to liquid/mass ratio;
3) mixed slurry is carried out spray drying and balling-up processing;
4) drying back material places baking furnace, under inert gas shielding, after 4～24 hours, to the sintered product screening, makes the phosphate-based positive electrode of said lithium ion battery in 500 ℃～900 ℃ insulations.
Wherein, the described phosphate precursor of step 1) is ferric phosphate, manganese phosphate or cobalt phosphate; Described metal salt solution is ferric chloride solution, iron nitrate solution, manganese chloride solution, manganese nitrate solution, cobalt chloride solution or cobalt nitrate solution.
Step 2) the lithium source described in is lithium carbonate, lithium hydroxide or lithium acetate; Described carbon source is acetylene black, superP, ensaco, CNT, glucose, sucrose, citric acid, polyethylene glycol or carboxymethyl cellulose.
Inert gas described in the step 4) is argon gas or nitrogen.
The invention has the advantages that: through the sheet phosphate precursor of preparation nano thickness; With sheet precursor and lithium source, carbon source, solvent; Adopt spray-dired method to make lithium source, carbon source dry on the phosphate nano synusia, and form the spheric granules of micro-meter scale.Through inert gas shielding, it is the spherical phosphate-based positive electrode that nanometer sheet is formed that pyroreaction generates pattern again.The particle of this material is that the small pieces by nano thickness become nodularization, forms the micron order second particle, through the designing material pattern the one dimension diffusion of lithium ion is converted into the three dimensionality diffusion, has greatly improved LiMPO
4The conductivity of/C material has been improved its chemical property.LiFePO wherein
4/ C material discharges and recharges under the 10C multiplying power, and capability retention reaches 90%.
Description of drawings
Fig. 1 is prepared according to the methods of the invention LiFePO
4The rate charge-discharge curve of/C positive electrode;
Fig. 2 is prepared according to the methods of the invention LiFePO
4The XRD figure of/C positive electrode;
Fig. 3 is prepared according to the methods of the invention LiFePO
4The SEM figure of/C positive electrode;
Fig. 4 is the partial enlarged drawing of Fig. 3.
Embodiment
Below in conjunction with specific embodiment product of the present invention and preparation method thereof is elaborated.
Take by weighing iron chloride, deionized water, be formulated as the ferric chloride solution of 1mol/L.With the ferric chloride solution injection volume of 5L 1mol/L is the normal-pressure reaction kettle of 20L, opens and stirs, and speed of agitator is set at 100rpm; With peristaltic pump 5L 1mol/L phosphoric acid solution is squeezed into agitated reactor with the flow velocity of 100ml/min then; Adding ammoniacal liquor, to regulate pH be 2, leave standstill after 6 hours material be transferred to bottle,suction, suction filtration, wash be 8 to washings pH after; 150 ℃ of oven dry obtain FePO in baking oven
42H
2O.
With Li: the Fe atomic ratio is 1: 1, and carbon content is 5.5% to calculate, and takes by weighing Li
2CO
373.9g, FePO
42H
2O 373.6g, SuperP 25g, 950ml deionized water mixed 4 hours in planetary ball mill.Mix disposed slurry and carry out drying and balling-up processing with centrifugal spray dryer, the spray dryer inlet temperature is 350 ℃ ± 5 ℃, and outlet temperature is 240 ℃ ± 5 ℃.With dried powder in the blanket of nitrogen kiln 800 ℃ down behind the insulation 4h, screening obtains Li to sintered product
+The LiFePO of three dimensionality diffusion
4/ C positive electrode.
Specific discharge capacity is greater than 150mAh/g under the LiFePO 4 material 0.1C discharge-rate of present embodiment preparation, and the 10C specific discharge capacity reaches more than 90% of 1C.
Embodiment 2
Take by weighing manganese acetate, deionized water, the manganese acetate solution of preparation 1mol/L, it is the normal-pressure reaction kettle of 20L that the manganese acetate solution of 5L 1mol/L is injected volume; Open and stir, speed of agitator is set at 100rpm, with peristaltic pump 5L 1mol/L phosphoric acid solution is squeezed into agitated reactor with the flow velocity of 100ml/min; Adding ammoniacal liquor, to regulate pH be 3, react after 10 hours material to be transferred to bottle,suction, suction filtration, wash be 9 to washings pH after; 150 ℃ of oven dry obtain Mn in baking oven
3(PO
4)
23H
2O.
With Li: the Mn atomic ratio is 1.05: 1, and carbon content is 3% to calculate, and takes by weighing Li
2CO
377.6g, Mn
3(PO
4)
23H
2O 272.5g, molecular weight are 10000 polyethylene glycol 147g, and the 1500ml deionized water mixed in planetary ball mill 4 hours.Mix disposed slurry and carry out drying and balling-up processing, 350 ℃ ± 5 ℃ of spray dryer inlet temperatures, 240 ℃ ± 5 ℃ of outlet temperatures with centrifugal spray dryer.With dried powder in the argon atmospher kiln 500 ℃ down behind the insulation 16h, screening obtains Li to sintered product
+The LiMnPO of three dimensionality diffusion
4/ C positive electrode.
Specific discharge capacity is greater than 110mAh/g under the lithium manganese phosphate material 0.1C discharge-rate of present embodiment preparation, and the 1C specific discharge capacity is 100mAh/g, reaches more than 90% of 0.1C.
Embodiment 3
Take by weighing cobalt nitrate, deionized water, the cobalt nitrate solution of preparation 1mol/L, it is the normal-pressure reaction kettle of 20L that the cobalt nitrate solution of 5L 1mol/L is injected volume; Open and stir, speed of agitator is set at 100rpm, with peristaltic pump 5L 1mol/L phosphoric acid solution is squeezed into agitated reactor with the flow velocity of 100ml/min; Adding ammoniacal liquor adjusting pH is 4; React and after 12 hours material be transferred to bottle,suction, wash to washings pH be 8～9 back 150 ℃ of oven dry in baking oven, obtain Co
3(PO
4)
28H
2O.
With Li: the Co atomic ratio is 1.02: 1, and carbon content is 5% to calculate, and takes by weighing LiOH 73.1g, Co
3(PO
4)
28H
2O 510.8g, citric acid 161.4g, 1000ml deionized water mixed in planetary ball mill 4 hours.Mix disposed slurry and carry out drying and balling-up processing, 350 ℃ ± 5 ℃ of spray dryer inlet temperatures, 240 ℃ ± 5 ℃ of outlet temperatures with centrifugal spray dryer.With dried powder in high pure nitrogen atmosphere kiln 900 ℃ down behind the insulation 8h, screening obtains Li to sintered product
+The LiCoPO of three dimensionality diffusion
4/ C positive electrode.
Specific discharge capacity is greater than 105mAh/g under the cobalt phosphate lithium material 0.1C discharge-rate of present embodiment preparation, and the 1C specific discharge capacity is 90mAh/g, reaches more than 88% of 0.1C.
Fig. 1 is the 10C high power charging-discharging curve and the contrast of 0.1C charging and discharging curve of embodiment 1 preparation sample, and as can be seen from the figure discharge capacity is 90.6% of 0.1C discharge capacity (155.8mAh/g) up to 141.3mAh/g under the 10C multiplying power of sample.
Fig. 2 is the XRD figure of embodiment 1 preparation sample, and as can be seen from the figure sample degree of crystallinity is higher, is the olivine-type LiFePO4 of pure phase.
Fig. 3 is the SEM figure of embodiment 1 preparation sample, and as can be seen from the figure sample particle is spherical in shape, and even particle size distribution, is about about 15 μ m, and sphericity is very high.Can find out in the big multiplying power SEM photo that spheric granules is to be reunited by nano-sheet or column primary particle with forming.This special construction of material has been broken the restriction that Li+ only can spread on a dimension in lithium iron phosphate positive material, improved the conductivity of material greatly, so the material high rate performance has obtained significantly improving.
Claims (9)
1. phosphate-based positive electrode of lithium ion battery, it is characterized in that: its structural group becomes LiMPO
4/ C, wherein M is a metallic element, carbon content is 1～6% (wt%).
2. the phosphate-based positive electrode of lithium ion battery according to claim 1 is characterized in that: described metallic element M is Fe, Mn or Co.
3. the preparation method of claim 1 or the phosphate-based positive electrode of 2 described lithium ion batteries is characterized in that may further comprise the steps:
1) preparation phosphate precursor: dispose metal salt solution and the 1mol/L phosphoric acid solution of 1mol/L respectively, metal salt solution is injected agitated reactor, open and stir; Add the fluorocarbon surfactant of salting liquid volume 1%～5% metering, squeeze into phosphoric acid solution with the speed that is lower than 500ml/min, treat that phosphoric acid solution adds after; Adding ammoniacal liquor adjusting pH value is 2～4, more than the reaction 6h, then material is transferred to bottle,suction; Carry out suction filtration, washing; Wash to washings pH be 8～9, the oven dry, obtain the phosphate precursor;
2) place ball mill to mix with lithium source, carbon source, solvent 1～24 hour according to design proportion gained phosphate precursor; Wherein the mol ratio of metal and lithium is M: Li=1: 1～1.05; Carbon source is 1%～6% calculating by the product carbon content, Gu solvent is 1～20: 1 calculating according to liquid/mass ratio;
3) mixed slurry is carried out spray drying and balling-up processing;
4) drying back material places baking furnace, under inert gas shielding, after 4～24 hours, to the sintered product screening, makes the phosphate-based positive electrode of said lithium ion battery in 500 ℃～900 ℃ insulations.
4. preparation method according to claim 3 is characterized in that: the described phosphate precursor of step 1) is ferric phosphate, manganese phosphate or cobalt phosphate.
5. preparation method according to claim 3 is characterized in that: the described metal salt solution of step 1) is ferric chloride solution, iron nitrate solution, manganese chloride solution, manganese nitrate solution, cobalt chloride solution or cobalt nitrate solution.
6. preparation method according to claim 3 is characterized in that: the mixing speed of the described agitating device of step 1) is 100～700r/min.
7. preparation method according to claim 3 is characterized in that: step 2) described in the lithium source be lithium carbonate, lithium hydroxide or lithium acetate.
8. preparation method according to claim 3 is characterized in that: step 2) described in carbon source be acetylene black, superP, ensaco, CNT, glucose, sucrose, citric acid, polyethylene glycol or carboxymethyl cellulose.
9. preparation method according to claim 3 is characterized in that: the inert gas described in the step 4) is argon gas or nitrogen.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104701535A (en) * | 2013-12-05 | 2015-06-10 | 天津赫维科技有限公司 | Preparation method of lithium manganese phosphate material |
| CN104743536A (en) * | 2015-02-10 | 2015-07-01 | 常州普格纳能源材料有限公司 | Preparation method of phosphate anode material |
| CN106744778A (en) * | 2016-12-28 | 2017-05-31 | 湖北金泉新材料有限责任公司 | A kind of method that molten-salt growth method prepares lithium iron phosphate cathode material |
| CN106887586A (en) * | 2017-03-17 | 2017-06-23 | 成都新柯力化工科技有限公司 | The iron manganese phosphate electrode material of lithium battery and preparation method of a kind of carbon aerogels network |
| CN107887583A (en) * | 2017-10-30 | 2018-04-06 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of doped lithium iron phosphate anode material and preparation method thereof |
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|---|---|---|---|---|
| CN101172594A (en) * | 2007-10-11 | 2008-05-07 | 河北工业大学 | Process for producing iron phosphate for producing iron lithium phosphate material |
| CN101237043A (en) * | 2008-01-31 | 2008-08-06 | 东北师范大学 | Method for making ferrous lithium phosphate/carbon compound material of high active disorderly ferric phosphate |
| CN101693532A (en) * | 2009-10-16 | 2010-04-14 | 清华大学 | Method for preparing lithium ferrous phosphate |
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2012
- 2012-03-29 CN CN2012100876774A patent/CN102623695A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172594A (en) * | 2007-10-11 | 2008-05-07 | 河北工业大学 | Process for producing iron phosphate for producing iron lithium phosphate material |
| CN101237043A (en) * | 2008-01-31 | 2008-08-06 | 东北师范大学 | Method for making ferrous lithium phosphate/carbon compound material of high active disorderly ferric phosphate |
| CN101693532A (en) * | 2009-10-16 | 2010-04-14 | 清华大学 | Method for preparing lithium ferrous phosphate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104701535A (en) * | 2013-12-05 | 2015-06-10 | 天津赫维科技有限公司 | Preparation method of lithium manganese phosphate material |
| CN104743536A (en) * | 2015-02-10 | 2015-07-01 | 常州普格纳能源材料有限公司 | Preparation method of phosphate anode material |
| CN104743536B (en) * | 2015-02-10 | 2017-02-01 | 常州普格纳能源材料有限公司 | Preparation method of phosphate anode material |
| CN106744778A (en) * | 2016-12-28 | 2017-05-31 | 湖北金泉新材料有限责任公司 | A kind of method that molten-salt growth method prepares lithium iron phosphate cathode material |
| CN106887586A (en) * | 2017-03-17 | 2017-06-23 | 成都新柯力化工科技有限公司 | The iron manganese phosphate electrode material of lithium battery and preparation method of a kind of carbon aerogels network |
| CN106887586B (en) * | 2017-03-17 | 2018-11-20 | 江苏贝肯新材料有限公司 | A kind of the iron manganese phosphate electrode material of lithium battery and preparation method of carbon aerogels network |
| CN107887583A (en) * | 2017-10-30 | 2018-04-06 | 贝特瑞（天津）纳米材料制造有限公司 | A kind of doped lithium iron phosphate anode material and preparation method thereof |
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Application publication date: 20120801 |