CN102442654B - Method of preparing battery-grade lithium dihydrogen phosphate by recrystallized lithium hydroxide - Google Patents
Method of preparing battery-grade lithium dihydrogen phosphate by recrystallized lithium hydroxide Download PDFInfo
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- CN102442654B CN102442654B CN 201010502973 CN201010502973A CN102442654B CN 102442654 B CN102442654 B CN 102442654B CN 201010502973 CN201010502973 CN 201010502973 CN 201010502973 A CN201010502973 A CN 201010502973A CN 102442654 B CN102442654 B CN 102442654B
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- lithium hydroxide
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Abstract
The invention relates to a method for producing battery-grade lithium dihydrogen phosphate, belonging to the manufacturing technical field of the lithium dihydrogen phosphate. As commercially available industrial-grade lithium hydroxide has higher impurity content soluble impurities, the invention provides a new method for producing the battery-grade lithium dihydrogen phosphate aiming at the problem that the soluble impurities in the prior art are easily enriched, comprising the steps of: (1) preparation of recrystallized lithium hydroxide; (2) neutral reaction: reacting phosphoric acid withthe recrystallized lithium hydroxide according to a mol ratio of LiOH to H3PO4 being 1 : (1-1.1), adjusting a PH value to be 1-3, and obtaining a lithium dihydrogen phosphate solution; (3) evaporating concentration; (4) cooling, crystallization and separation; and (5) drying and packaging to obtain lithium dihydrogen phosphate products. The method of preparing the battery-grade lithium dihydrogenphosphate by the recrystallized lithium hydroxide has the advantages of a short technical process, a simple operation and low cost. The obtained battery-grade lithium dihydrogen phosphate products have few impurities (Na, K, SO4(2-) and Cl(1-) in the products are all less than 20 ppm) and stable quality, and can be suitable for preparing a cathode material of a lithium ion battery.
Description
One, technical field
The present invention relates to a kind of production method of battery-grade lithium dihydrogen phosphate, belong to monometallic manufacturing technology field.
Two, background technology
Lithium cell is a kind of novel battery of the eighties of last century rise nineties, comprising lithium primary battery and lithium secondary battery.Along with popularizing and application of the portable small-sized electrical equipment such as mobile phone, notebook computer, lithium secondary battery also develops thereupon and popularizes.Its positive electrode material mainly contains cobalt acid lithium, lithium manganate, lithium nickelate and ternary material etc.(A is basic metal to disclose first AyMPO4 from the NTT of Japan in 1996, M is both combinations of CoFe: after the anode material of lithium battery of olivine structural LiFeCOPO4), the Research Groups such as the vertical John.B.Goodenough of university of Texas, USA in 1997, also then reported iron lithium phosphate reversibility the characteristic of the lithium of moving into, so that this material has been subject to great attention, and cause widely research and rapidly development.With traditional lithium ion secondary battery anode material, the lithium manganate of spinel structure is compared with the cobalt of laminate structure acid lithium, it is good that iron lithium phosphate has a Stability Analysis of Structures security, energy density is high, the raw material source is more extensive, price is cheaper and non-environmental-pollution, the characteristics such as the life-span is long are the preferred material as lithium dynamical battery.At present the main production method of iron lithium phosphate has two kinds of high temperature solid-state method and liquid phase methods, and high temperature solid-state method is the method for present major industry production, and its raw material is used Quilonum Retard, lithium hydroxide and monometallic according to the difference of technique.Monometallic is as the raw material of producing iron lithium phosphate, and major advantage has been to avoid the synthetic middle primary ammonium phosphate that uses of other method, avoids producing the problem of a large amount of ammonia contaminate environment.The main method of producing at present monometallic has neutralisation and extraction process.The used extraction agent of extraction process is one or more mixture in methyl alcohol, ethanol, propyl alcohol, Virahol, the glycerol, and complex process, poor stability, cost are high.Neutralisation exists pilot process need increase the additive removal of impurities, and technical process is long, and the preparation process of additive own is complicated, energy consumption is high, cost is high, such as Fig. 1.
Three, summary of the invention
The invention belongs to neutralisation, order ground is the loaded down with trivial details problem of long flow path, impurity enriched, removal of impurities that solves existing technique, take lithium hydroxide is removed soluble impurity with the easy mode of recrystallization, avoid soluble impurity to enter into the monometallic production system and cause the problems referred to above, can simplify the constant product quality of technique, reduction cost and output.
Technical scheme of the present invention: the lithium hydroxide recrystallization is removed soluble impurity such as K, Na, SO
4 2-, Cl
-Deng.Recrystallization lithium hydroxide and phosphoric acid neutralization are produced battery-grade lithium dihydrogen phosphate.Its reaction equation is: LiOHH
2O+H
3PO
4=LiH
2PO
4+ 2H
2O.It is characterized in that may further comprise the steps:
1, recrystallization lithium hydroxide preparation: with the industrial hydrogen Lithium Oxide 98min with the press filtration of 5: 1 usefulness pure water of liquid-solid ratio stirring and dissolving, obtain the clean liquid of lithium hydroxide, clean liquid is evaporated to the 1/5-1/4 of original volume, being cooled to 20-30 degree centigrade separates, obtain recrystallization lithium hydroxide and mother liquor, to stir during with the pure water stirring and dissolving fully, time is 0.5-1 hour, whizzer need run up 10-15 minute during centrifugation, to guarantee recrystallization lithium hydroxide master content＞95%, its impurity need meet Na≤0.003%, K≤0.003% simultaneously, Ca≤0.005%, CO
2≤ 0.5%, Fe≤0.001%, SO
4 2-≤ 0.005%, detect the soluble impurity in the lithium hydroxide mother liquor, content is back to dissolving press filtration operation when low, with the wet Trilithium phosphate of phosphatase reaction preparation, being prepared into the Trilithium phosphate finished product through separating drying and packaging, react mol ratio LiOH: H when content is high
3PO
4=3: 1-1.1.
2, neutralization reaction: with phosphoric acid and pure water with 1: 3 stirring and evenly mixing of weight ratio, in molar ratio LiOH: H
3PO
4=1: 1-1.1 slowly adds the recrystallization lithium hydroxide, after complete reaction, with lithium hydroxide or phosphoric acid neutralization solution is regulated pH value to 1-3, obtain monometallic solution, in and the time note adding first phosphoric acid back end hydrogenation Lithium Oxide 98min, the adding speed of control lithium hydroxide is avoided the excessive corrosion glass-lined equipment of basicity.
3, evaporation concentration: will mix up the monometallic solution press filtration of pH value, with the filtrate cycle press filtration until after limpid again with its press filtration to the concentration response still, avoid insoluble impurities to affect product quality, the clean liquid that obtains is carried out evaporation concentration, concentrated temperature is controlled at 115-135 degree centigrade.
4, crystallisation by cooling separates: carry out liquid-solid separation after solution is cooled to 20-40 degree centigrade, obtain the wet product of monometallic and monometallic mother liquor, in the process of cooling, want a direct-open to stir, the monometallic crystal grain that generates during with the assurance cooling is even, detect the soluble impurity in the monometallic mother liquor, when the monometallic that it is can not output qualified that its soluble impurity raises, Trilithium phosphate is made in the reaction of itself and lithium hydroxide and the liquid-solid drying and packaging that separates becomes the Trilithium phosphate product, mol ratio LiOH: LiH
2PO
4=2: 1-1.1, when can the output qualified monometallic of its soluble impurity, return the preparation of carrying out monometallic solution to neutralization.
5, drying and packaging: with the wet product of monometallic drying under-0.09 to-0.03Mp vacuum, bake out temperature is 105-130 degree centigrade, drying time is 2-4 hour, obtain the battery-grade lithium dihydrogen phosphate product, when oven dry finishes, to open first vacuum tightness that the vacuum blow-off valve reduces dryer to-0.03Mp, and then close vacuum pump, prevent the water Suction contamination product in the vacuum pump.
The invention has the advantages that, soluble impurity and soluble impurity are all removed with physical purification method, so the soluble impurity in the mother liquor is very low, cycle index improves greatly, and the periodic crystallisation when avoiding processing mother liquor has reduced energy consumption and cost, the while shortened process, improved the rate of recovery, quality product is more stable, such as Fig. 2.
Four, description of drawings
Fig. 1 is existing technical process
Fig. 2 is technical process of the present invention
Five, embodiment
Embodiment 1:
Referring to Fig. 2, the method that present embodiment 1 prepares battery-grade lithium dihydrogen phosphate comprises the steps:
(1) 800kg industrial hydrogen Lithium Oxide 98min is joined in the 4000L pure water, fully stir, after lithium hydroxide dissolves fully, filter, remove insoluble impurities, obtain the clean liquid of lithium hydroxide;
The clean liquid that (2) will obtain evaporates, the evaporated vapor pressure-controlling is at 0.1-0.3Mp, the excessive velocities that avoids evaporating lithium hydroxide solution overflows, clean liquid evaporation concentration is cooled off to 1000L, cooling temperature is controlled at 20-30 degree centigrade, separate with whizzer after cooling is finished, obtain 640kg recrystallization lithium hydroxide and lithium hydroxide mother liquor after the separation, the lithium hydroxide mother liquor returns the dissolution filter operation;
(3) with 300kg PHOSPHORIC ACID TECH.GRADE (content 85%) and 900L pure water stirring and evenly mixing, add recrystallization lithium hydroxide 100kg and neutralize, fully stir, stirring velocity is 60 rev/mins.The fully rear pH value that detects of question response is regulated control pH value to 1.8 with PHOSPHORIC ACID TECH.GRADE or recrystallization lithium hydroxide.
(4) regulate pH value after, the beginning heating evaporation, stopped heating when being evaporated to 125 degrees centigrade begins to cool down.
(5) carry out liquid-solid separation after being cooled to 30 degrees centigrade, obtain the wet product of 165kg monometallic and monometallic mother liquor, mother liquid recycling;
(6) the wet product of monometallic are fed in the vacuum double-cone dryer, open vacuum pump, heating.Be heated to 105 degrees centigrade of beginning timing, dry stopped heating after 3 hours, logical circulating water discharging packing obtains the battery-grade lithium dihydrogen phosphate finished product, and quality product sees Table 1.
Embodiment 2:
Referring to Fig. 2, the method that present embodiment 2 prepares battery-grade lithium dihydrogen phosphate comprises the steps:
(1) 800kg industrial hydrogen Lithium Oxide 98min is joined in the 4000L pure water, fully stir, after lithium hydroxide dissolves fully, filter, remove insoluble impurities, obtain the clean liquid of lithium hydroxide;
The clean liquid that (2) will obtain evaporates, the evaporated vapor pressure-controlling is at 0.1-0.3Mp, the excessive velocities that avoids evaporating lithium hydroxide solution overflows, clean liquid evaporation concentration is cooled off to 1000L, cooling temperature is controlled at 20-30 degree centigrade, separate with whizzer after cooling is finished, obtain 640kg recrystallization lithium hydroxide and lithium hydroxide mother liquor after the separation, the lithium hydroxide mother liquor returns the dissolution filter operation;
(3) with 300kg PHOSPHORIC ACID TECH.GRADE (content 85%) and 900L pure water stirring and evenly mixing, add recrystallization lithium hydroxide 105kg and neutralize, fully stir, stirring velocity is 60 rev/mins.The fully rear pH value that detects of question response is regulated control pH value to 2.5 with PHOSPHORIC ACID TECH.GRADE or recrystallization lithium hydroxide.
(4) regulate pH value after, the beginning heating evaporation, stopped heating when being evaporated to 130 degrees centigrade begins to cool down.
(5) carry out liquid-solid separation after being cooled to 30 degrees centigrade, obtain the wet product of 172kg monometallic and monometallic mother liquor, mother liquid recycling;
(6) the wet product of monometallic are fed in the vacuum double-cone dryer, open vacuum pump, heating.Be heated to 105 degrees centigrade of beginning timing, dry stopped heating after 3 hours, logical circulating water discharging screening packing obtains the battery-grade lithium dihydrogen phosphate finished product, and quality product sees Table 1.
Table 1: battery-grade lithium dihydrogen phosphate embodiment 1,2 analytical resultss
| Test item | Embodiment 1 | Embodiment 2 |
| LiH 2PO 4(％) | 99.60 | 99.71 |
| Na(％) | 0.0008 | 0.001 |
| K(％) | 0.001 | 0.001 |
| Ca(％) | 0.001 | 0.0011 |
| Pb(％) | 0.0004 | 0.0003 |
| Fe(％) | 0.0004 | 0.0005 |
| SO 4 2-(％) | 0.0015 | 0.0012 |
| Cl -(％) | 0.001 | 0.001 |
| PH | 3.68 | 3.74 |
| Water-insoluble (%) | 0.004 | 0.004 |
| Moisture | 0.14 | 0.11 |
Claims (1)
1. utilize the recrystallization lithium hydroxide to prepare the production method of battery-grade lithium dihydrogen phosphate, it is characterized in that: the preparation of battery-grade lithium dihydrogen phosphate may further comprise the steps:
(1) recrystallization lithium hydroxide preparation: with the industrial hydrogen Lithium Oxide 98min with the press filtration of 5: 1 usefulness pure water of liquid-solid ratio stirring and dissolving, obtain the clean liquid of lithium hydroxide, clean liquid is evaporated to 1/5～1/4 of original volume, is cooled to 20～30 degrees centigrade and separates, obtain recrystallization lithium hydroxide and lithium hydroxide mother liquor;
Main content and the foreign matter content of described recrystallization lithium hydroxide need reach following requirement:
The high and low respectively method to its processing of the content of the soluble impurity of described lithium hydroxide mother liquor is as follows:
When its soluble impurity raises the recrystallization lithium hydroxide that carries out the recrystallization output can not satisfy the main content of described recrystallization lithium hydroxide and foreign matter content and require the time, itself and phosphatase reaction are made Trilithium phosphate and the liquid-solid drying and packaging that separates become the Trilithium phosphate product, mol ratio LiOH: H
3PO
4=3: 1～1.1;
When the recrystallization lithium hydroxide that carries out the recrystallization output when its soluble impurity can satisfy the main content of described recrystallization lithium hydroxide and foreign matter content and requires, namely be prepared into the recrystallization lithium hydroxide;
(2) neutralization reaction: with phosphoric acid and pure water with 1: 3 stirring and evenly mixing of weight ratio, in molar ratio LiOH: H
3PO
4Add recrystallization lithium hydroxide at=1: 1～1.1, with lithium hydroxide or phosphoric acid neutralization solution regulated pH value to 1～3 after complete reaction, obtains monometallic solution;
(3) evaporation concentration: will mix up the monometallic solution press filtration of pH value, the clean liquid that obtains is carried out evaporation concentration, concentrated temperature is controlled at 115～135 degrees centigrade, obtains the monometallic concentrated solution;
(4) crystallisation by cooling separates: the monometallic concentrated solution is cooled off in reactor, and temperature is down to 20～40 degrees centigrade and is carried out liquid-solid separation, obtains the wet product of monometallic and monometallic mother liquor;
The high and low respectively method to its processing of the content of the soluble impurity of described monometallic mother liquor is as follows:
When the monometallic that it is can not output qualified that its soluble impurity raises, and Trilithium phosphate is made in the lithium hydroxide reaction and the liquid-solid drying and packaging that separates becomes the Trilithium phosphate product, mol ratio LiOH: LiH with it
2PO
4=2: 1～1.1;
When can the output qualified monometallic of its soluble impurity, it is returned the preparation of carrying out monometallic solution to neutralization reaction;
(5) drying and packaging: the wet product of monometallic that obtain are dry under vacuum state, oven dry vacuum tightness is-0.03 to-0.09Mpa, and bake out temperature is 105～130 degrees centigrade, and drying time is 2～4 hours, pack after oven dry is finished, obtain the monometallic product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269806A (en) * | 2008-05-06 | 2008-09-24 | 四川天齐锂业股份有限公司 | Preparation for battery level lithium dihydrogen phosphate |
| CN101327919A (en) * | 2007-06-19 | 2008-12-24 | 比亚迪股份有限公司 | Synthetic method of lithium dihydrogen phosphate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327919A (en) * | 2007-06-19 | 2008-12-24 | 比亚迪股份有限公司 | Synthetic method of lithium dihydrogen phosphate |
| CN101269806A (en) * | 2008-05-06 | 2008-09-24 | 四川天齐锂业股份有限公司 | Preparation for battery level lithium dihydrogen phosphate |
Non-Patent Citations (2)
| Title |
|---|
| 浅谈高纯碳酸锂的制备方法;王运其;《新疆有色金属》;20091231;第92-93页 * |
| 王运其.浅谈高纯碳酸锂的制备方法.《新疆有色金属》.2009,第92-93页. |
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