CN102311110B - Complete cycle preparation method of lithium iron phosphate by using lithium ores as lithium source - Google Patents

Complete cycle preparation method of lithium iron phosphate by using lithium ores as lithium source Download PDF

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CN102311110B
CN102311110B CN2011103205160A CN201110320516A CN102311110B CN 102311110 B CN102311110 B CN 102311110B CN 2011103205160 A CN2011103205160 A CN 2011103205160A CN 201110320516 A CN201110320516 A CN 201110320516A CN 102311110 B CN102311110 B CN 102311110B
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lithium
solution
preparation
ferrous
combination
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CN102311110A (en
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王平
黄春莲
金鹏
高宜宝
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Tianqi lithium industry (Shehong) Co., Ltd.
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Sichuan Tianqi Lithium Industriesinc
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Priority to PCT/CN2012/074336 priority patent/WO2013056543A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention relates to a complete cycle preparation method of lithium iron phosphate by using lithium ores as a lithium source, comprising the following steps: carrying out calcining, acidifying, leaching, purifying and separating on the lithium ores to obtain a primary lithium liquid, carrying out conversion and refrigeration, filtering and washing, evaporative concentration on the primary lithium liquid to obtain a lithium liquid for synthesis, letting the lithium liquid for synthesis, a ferrite solution, and a phosphor source solution be subject to liquid phase synthesis, and calcining to obtain the carbon coated lithium iron phosphate. According to the invention, cooling crystallization, separation, drying and other steps in the preparation of lithium iron phosphate with lithium ores are left out, and the byproducts obtained by evaporative concentration, filtering and separating are recycled, so that the utilization rate of resource is increased, and the cost is saved; and the prepared lithium iron phosphate has the characteristics of high purity, excellent electrochemical performance and the like, so that the circular economy is realized.

Description

A kind of complete circulation preparation method who produces LiFePO 4 take the lithium ore deposit as the lithium source
Technical field
The invention belongs to the lithium ion battery material field, be specifically related to a kind of complete circulation preparation method who produces LiFePO 4 take the lithium ore deposit as the lithium source.
Background technology
Find the phosphate metal lithium from Goodenough study group in 1994, A.K.Padhi reported first olivine-type LiFePO 4 had had since the lithium of the taking off embedding lithium function in 1997, LiFePO 4 is high with its specific storage, have extended cycle life, safety, raw material sources are abundant and cheap, advantages of environment protection is widely studied, and becomes the desirable positive electrode material of producing lithium ion battery.In recent years, under the energetically support of national governments, the Commercialization application degree of ferrous phosphate lithium dynamical battery improves day by day.
Existing LiFePO 4 preparation method comprises that high temperature solid phase synthesis (for example, A.K.Padhi, K.S.Nanjundaswamy, J.B.Goodenough, Phospho-Olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries, J.Electrochem.Soc., 1997,144,1188-1194), low temperature liquid phase synthesis method (such as CN03102665.6), liquid-phase coprecipitation, hydrothermal synthesis method etc.Wherein, there is the easy oxidation of ferrous ion in the high temperature solid-state method production process, Fe 3+Be difficult for being reduced to fully Fe 2+Thereby, exist the resistance of LiFePO 4 high, the defectives such as the consistence of product and less stable.And, the starting raw material of the preparation LiFePO 4 that uses in these synthetic methods is generally lithium salts, for example, CN200510132431.4 discloses a kind of preparation method of lithium enriched lithium ion phosphate powder, take Quilonum Retard, lithium oxalate, Lithium Acetate or lithium nitrate as the lithium source; ZL200410017382.5 discloses the preparation method of the anode composite material of lithium ion battery of containing lithium iron phosphate salt-carbon, take Quilonum Retard, lithium hydroxide, lithium oxalate, Lithium Acetate or Trilithium phosphate as the lithium source; CN200610136737.1 discloses a kind of method of synthesizing Nano level powder of lithium iron phosphate, take Quilonum Retard, lithium hydroxide, lithium nitrate, lithium chloride or monometallic as the lithium source; CN200610035986.1 discloses the method for high temperature solid-state synthesizing iron lithium phosphate positive electrode material, take Quilonum Retard, lithium fluoride, Lithium Acetate, lithium hydroxide or lithium nitrate as the lithium source.Yet, the production cost for preparing LiFePO 4 take lithium salts as the lithium source is very expensive, also need independently lithium salts processing, refining, purifying, circulation, the links such as storage, and need further recycling lithium salts, byproduct in the LiFePO 4 production process, not only increase production cost, and resource utilization is not high, and bring environmental pollution, the production in lithium source can not well the lithium ore deposit be prepared and organic linking is carried out in the production of LiFePO 4, and then take full advantage of the lithium ore deposit and prepare the byproduct of lithium source in producing and carry out complete cyclic production with the byproduct in the LiFePO 4 production, the realization recycling economy.
At present, produce both at home and abroad and use lithium, except lithium is carried in the salt lake, the main required lithium salts of preparation that from the triphane of pegmatite type, extracts.The commercial run of producing lithium salts from the lithium ore comprises: vitriolate of tartar method, lime method, sulfuric acid process and soda ash are pressed hot extraction etc.China's ore is carried lithium and is mainly adopted sulfuric acid process to produce lithium salts from triphane, and its preparation process comprises the steps such as roasting, acidifying, leaching, neutralization, conversion, evaporation, crystallization, filtration.And, all be to adopt Wingdale (CaCO in the prior art 3) regulate the pH value, so that produce a large amount of Ca in the slurry after the neutralization 2+Plasma, and part generates Li 2CO 3Precipitate and loss part Li +In addition, produce a large amount of byproducts such as water of condensation in the evaporating concentration process and do not fully utilized, cause production cost higher.
For this reason, a kind of preparation method of more economic, effective LiFePO 4 need to be sought in this area, both can effectively reduce the production cost of LiFePO 4, can guarantee that again LiFePO 4 has excellent use properties.
Summary of the invention
The object of the present invention is to provide a kind of complete circulation preparation method who produces LiFePO 4 take the lithium ore deposit as the lithium source, complete circulation preparation method of the present invention need not to carry out that numerous and diverse lithium salts is refining, purification process, and part has been omitted sulfuric acid process and prepared crystallisation by cooling, separation, removal of impurities, drying and other steps in the lithium salts; And, the water of condensation byproduct that produces in the preparation lithium source procedure is cycled to used in preparation ferrous salt solution or phosphorus source solution, and the lithium byproduct that contains in the LiFePO 4 production is cycled to used in again the process that the lithium ore deposit prepares the lithium source, and byproduct is turned waste into wealth, realize recycling economy, not only saved cost but also environmental protection.
The technical scheme that the present invention addresses the above problem: process following steps:
(1) with the calcining of lithium ore deposit, acidifying, leaching, purification, separation, the filtrate evaporation concentration makes primary lithium liquid;
(2) primary lithium liquid is transformed freezing, filter, washing, the filtrate evaporation concentration makes reaction lithium liquid;
(3) will react with lithium liquid and ferrous salt solution, phosphorus source solution and carry out after the liquid phase building-up reactions obtains LiFePO 4, filter, washing, to filter cake washing liquid, do not detect lithium ion, in filter cake, add an amount of water, it is diluted to mud, add the glycogen material, calcining namely gets the ferrousphosphate lithium material that carbon coats;
Wherein, the condensate water circulatory that produces in step (1) and the described evaporating concentration process of step (2) is used at least a of preparation phosphorus source solution, ferrous salt solution; Collect filtrate and filter cake washing liquid in the step (3), namely contain the solution of lithium salts or reclaim filtrate, it is returned the leaching operation of step (1), in addition recycle;
Step (2) described " transforming freezing " refers to add sodium salt in the primary lithium liquid Li in the primary lithium liquid 2SO 4With the sodium salt reaction, produce another kind of lithium salts and Na 2SO 4, again with the cooling of gained reaction soln, thereby so that the sulfate crystal that generates is separated out, filtering separation is removed.
In the preferred technical solution of the present invention, described lithium ore deposit is selected from any or its combination of triphane, amblygonite, montebrasite, lithionite, petalite.
In the preferred technical solution of the present invention, the described reaction of step (2) is preferably 26.2g/L with the lithium content 25～27g/L in the lithium liquid.
In the preferred technical solution of the present invention, the Ca of the described reaction of step (2) in the lithium liquid 2+, Mg 2+, Cl -, K +, Cu 2+, Pb 2+Any content be not higher than 0.01%.
In the preferred technical solution of the present invention, Fe in the described ferrous salt solution 2+Concentration is 54-59g/L, is preferably 55.8g/L.
In the preferred technical solution of the present invention, PO in the solution of described phosphorus source 4 3-Concentration is 680～800g/L, is preferably 719.2g/L.
In the preferred technical solution of the present invention, the volume ratio that participates between liquid reactive lithium solution, ferrous salt solution, the phosphorus source solution is 2.5～3.5: 3～4: 0.3～0.7, and preferred volume ratio is 3: 3.5: 0.5.
In the preferred technical solution of the present invention, in step (3), will evenly mix with lithium solution, ferrous salt solution and phosphorus source solution for the metal salt solution that mixes, carry out the liquid phase building-up reactions.
In the preferred technical solution of the present invention, the metal salt solution that be used for to mix is selected from any or its combination of the metal salt solution of Co, Ni, Al, Zr.
In the preferred technical solution of the present invention, the ferrous salt raw material of preparing described ferrous salt solution is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate.
In the preferred technical solution of the present invention, the phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
Step (2) transforms when freezing, and the sodium salt that adds in the primary lithium liquid is selected from any or its combination in yellow soda ash, sodium hydroxide, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, sodium-chlor, sodium oxalate, the SODIUMNITRATE; Be preferably any or its combination in sodium-chlor, the sodium hydroxide.Correspondingly, the another kind of lithium salts that generates is any or its combination in Quilonum Retard, lithium hydroxide, monometallic, Trilithium phosphate, lithium chloride, lithium oxalate, the lithium nitrate.In the preferred technical solution of the present invention, the described glycogen material of step (3) is selected from any or its combination of sucrose, glucose, lactose.
In the preferred technical solution of the present invention, filtrate in the step (3) is namely contained the solution of lithium salts, and the solution that contains lithium salts is selected from any or its combination in lithium sulfate solution, Quilonum Retard solution, lithium hydroxide solution, monometallic solution, Trilithium phosphate solution, lithium chloride solution, lithium oxalate solution, the lithium nitrate solution.
In the preferred technical solution of the present invention, the preparation process of primary lithium liquid comprises the steps:
After A, lithium ore deposit place 1100～1380 ℃ of lower calcinings, in the lithium ore deposit, be to add sulfuric acid in the lithium ore deposit of 1: 4～7 (w/w) after calcining to carry out acidification by acid material ratio; In the lithium ore deposit, be 2-3 by liquid-solid ratio: 1 (w/w) adds entry or reclaims filtrate in acidification liquid, regulate pH value to 5.7～6.2, leaves standstill, and filters, and gets mother liquor 1;
B, adjusting mother liquor 1pH 8.5～9.7 leave standstill, and filter, and get mother liquor 2;
C, adjusting mother liquor 2pH 10～10.8 leave standstill, and filter, and get mother liquor 3;
Ca in D, the detection mother liquor 3 2+Concentration adds equimolar Na 2CO 3, stir, leave standstill, filter, get mother liquor 4;
E, evaporation concentration mother liquor 4 are to its Li +Concentration is 65～75g/L, filters, and gets mother liquor 5, and wherein, the water of condensation that produces in the evaporating concentration process is used for any or its combination of preparation ferrous salt solution, phosphorus source solution.
In the preferred technical solution of the present invention, reaction comprises the steps: with the preparation process of lithium liquid
SO in a, the detection mother liquor 5 4 2-Concentration adds an amount of sodium salt, with the SO in the mother liquor 5 4 2-All change into Na 2SO 4Stir, crystallisation by cooling, filter, mother liquor 6, wherein, described sodium salt is selected from any or its combination in yellow soda ash, sodium-chlor, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, sodium hydroxide, sodium oxalate, the SODIUMNITRATE, be preferably any or its combination in sodium-chlor, the sodium hydroxide, preferred cooling temperature is-15 ℃～0 ℃;
B, evaporation concentration mother liquor 6, containing the lithium amount to it is 25-27g/L, preferably its to contain the lithium amount be 26.2g/L, must react and use lithium solution, wherein, the water of condensation that produces in the evaporating concentration process is used for any or its combination of preparation ferrous salt solution, phosphorus source solution.
In the preferred technical solution of the present invention, described liquid phase synthesis condition is that reaction lithium solution, ferrous salt solution, phosphorus source solution adding reactor with the reaction aequum are heated to 150～220 ℃, be incubated 220～720 minutes, after the cooling, filter, get filter cake, for subsequent use, simultaneously, the filtrate of collecting is returned the leaching operation of primary lithium liquid, in addition recycle.
In the preferred technical solution of the present invention, washing described in the step (3) refers to wash to filter cake washing liquid and do not detect lithium ion, gets filter cake, and is for subsequent use, simultaneously, filtrate returned the leaching operation of primary lithium liquid, in addition recycle.
" not detecting lithium ion in the filter cake washing liquid " of the present invention refers to that the lithium ion content in the filter cake washing liquid is not higher than 0.01%.
In the preferred technical solution of the present invention, in the step (3) in cleaning filter cake the add-on of glycogen material be preferably 10wt% for cleaning 5～20wt% of filter cake solid content.
In the preferred technical solution of the present invention, calcining is under the provide protection of protective gas described in the step (3), and the even hybrid dry matter of calcining glycogen material and filter cake under 650～1000 ℃ of conditions is to make the LiFePO 4 of carbon coating.
In the preferred technical solution of the present invention, protective gas of the present invention is selected from any or its combination of argon gas, nitrogen, hydrogen.
In the preferred technical solution of the present invention, the preparation process of mother liquor 1 comprises the steps: to calcine the lithium ore deposits 50～300 minutes under 1100～1380 ℃, cooling, levigate, in the lithium ore deposit, carried out acidification 50-200 minute than adding sulfuric acid in the lithium ore deposit of 1: 4～7 (w/w) after calcining by the acid material; In the lithium ore deposit, be that 2～3: 1 (w/w) adds water or reclaim filtrate by liquid-solid ratio, regulate pH value to 5.7～6.2, stirred 35～50 minutes, leave standstill, filter, collect filtrate, namely get mother liquor 1.
In the preferred technical solution of the present invention, the calcination time under the provide protection of protective gas is 3～15 hours.
In the preferred technical solution of the present invention, the material of regulating pH is selected from any or its combination of sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, is preferably any or its combination of sodium hydroxide, yellow soda ash.
In the preferred technical solution of the present invention, described liquid phase building-up reactions is carried out in confined conditions, effectively to prevent the oxidation of Fe2+.
Another object of the present invention is to provide a kind of LiFePO 4 of carbon coating, complete preparation method prepares by circulation of the present invention.
In the preferred technical solution of the present invention, the purity of the LiFePO 4 that described carbon coats is not less than 99.97%, and preferred 1C specific storage is not less than 141mAh/g, more preferably Ca in the LiFePO 4 of carbon coating 2+, Mg 2+, SO4 2-, Cl -, Na +, K +, Cu 2+, Pb 2+Any content is not higher than 0.01%.
The LiFePO 4 that the carbon that another object of the present invention is to that the present invention is made coats is preferred for preparing the application in the lithium-ion-power cell material for the preparation of the application in the lithium ion battery material.
In order clearly to explain protection scope of the present invention, the present invention carries out description below to following term:
" primary lithium liquid " of the present invention refer to by produce in the lithium ore deposit through rough purification, separate the lithium solution make.
" reaction lithium liquid " of the present invention claims again " building-up reactions lithium liquid ", " reaction order lithium liquid ", refers to be directly used in the lithium solution that participates in the liquid phase building-up reactions.
" reclaim filtrate " of the present invention refers to the filtrate of collecting in the LiFePO 4 liquid phase building-up process, the wash filtrate of perhaps collecting in the LiFePO 4 filter cake washing process, " the reclaiming filtrate " of collecting can be returned the leaching operation of primary lithium liquid, in addition recycle.
" the even hybrid dry matter of glycogen material and filter cake " of the present invention refers to add an amount of water in the LiFePO 4 filter cake after cleaning, it is diluted to mud, the glycogen material that adds again filter cake solid content 5～20wt.%, after evenly mixing, dry, the even drying composite of gained, wherein, the add-on of preferred glycogen material is 10wt.%.
" solution that contains lithium salts " of the present invention refers to the lithium salt solution that generates in the LiFePO 4 production process, wherein, described lithium salt solution is selected from any or its combination of lithium sulfate solution, Quilonum Retard solution, lithium hydroxide solution, monometallic solution, Trilithium phosphate solution, lithium chloride solution, lithium oxalate solution, lithium nitrate solution.
" transforming freezing " described in the step of the present invention (2) refers to add sodium salt in primary lithium liquid, makes the Li in the primary lithium liquid 2SO 4With the sodium salt reaction, produce another kind of lithium salts and Na 2SO 4Again the gained reaction soln is cooled off, thereby so that the sulfate crystal that generates is separated out, be isolated by filtration and remove, must contain lithium mother liquor (being mother liquor 6), wherein, described sodium salt is selected from any or its combination in yellow soda ash, sodium hydroxide, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, sodium-chlor, sodium oxalate, the SODIUMNITRATE, is preferably any or its combination in sodium-chlor, the sodium hydroxide; Described another kind of lithium salts comprises any or its combination in Quilonum Retard, lithium hydroxide, monometallic, Trilithium phosphate, lithium chloride, lithium oxalate, the lithium nitrate.
Except as otherwise noted, per-cent of the present invention is weight percentage.
The present invention uses other pH value Auto-regulators (such as any or its combination in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood) instead and replaces CaCO 3, avoid in reaction system, bringing into a large amount of Ca 2+, and adopt classification to regulate the pH value and carry out classification and staticly settle, can effectively remove Ca 2+, Mg 2+, SO4 2-Deng.
The present invention is with the Ca in the yellow soda ash precipitation solution 2+, Mg 2+Deng impurity, it is thoroughly removed by filter, make reaction lithium solution.
The present invention reacts with lithium concentration and foreign matter content thereof in the lithium solution by rationally control, and form needs according to the preparation of LiFePO 4, with reaction with organically mating between the phosphoric acid solution concentration of the lithium concentration in the lithium solution and participation liquid phase building-up reactions, the ferrous iron solution concentration, can effectively reduce take the lithium ore deposit as lithium source preparation feedback with the purifying in the lithium solution process, make with extra care and production cost that evaporation concentration is increased.
Compared with prior art, the complete circulation preparation method for the production of LiFePO 4 has following advantage take the lithium ore deposit as the lithium source in the present invention:
1, circulation set technique of the present invention can form needs according to the preparation of LiFePO 4, lithium concentration or its foreign matter content of control reaction in the lithium solution, part has been omitted crystallisation by cooling that sulfuric acid process prepares the lithium salts process, separation and the operation such as dry, and shortened evaporation concentration time of mother liquor, saved the cost of marketing of lithium salts, reduce the difficulty of the refining clarification of lithium salts, significantly reduced production cost;
2, in addition recycle of the byproduct in the circulation set technique (water of condensation that evaporation concentration produces, the synthetic lithium-containing solution byproduct that generates of liquid phase etc.), omitted the recycling operation of byproduct, reduce even avoided the discharging of waste water, save cost for wastewater treatment, significantly improve resource utilization, significantly reduce production costs, realize simultaneously recycling economy;
3, the present invention uses other pH value Auto-regulators (such as any or its combination in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood) instead and replaces CaCO 3, avoid in reaction system, bringing into a large amount of Ca 2+, and adopt classification to regulate the pH value and carry out classification and staticly settle, can effectively remove Ca 2+, Mg 2+, SO4 2-Deng;
4, the present invention is with the Ca in the yellow soda ash precipitation solution 2+, Mg 2+Deng impurity, it is thoroughly removed, make reaction lithium solution;
5, the fine removal of this circulation set technique and controlled the Ca in the LiFePO 4 2+, Mg 2+, SO4 2-, Cl -, Na +, K +, Cu 2+, Pb 2+Deng foreign matter content, the advantages such as the LiFePO 4 of preparation gained has that purity is high, chemical property is excellent, stable, high conformity, the 1C loading capacity can reach more than the 140mAh/g;
6, the complete circulation technology of the present invention comprehensive cost that can save LiFePO 4 reaches more than 12000 yuan/tons.
Description of drawings
Fig. 1 produces the complete circulation preparation technology general flow chart of LiFePO 4 as the lithium source take the lithium ore deposit.
Fig. 2 produces the complete circulation preparation technology flow process detail drawing of LiFePO 4 as the lithium source take the lithium ore deposit.
The X ray diffracting spectrum of the LiFePO 4-carbon composite cathode material of Fig. 3 embodiment 2 preparations.
Embodiment
The object of the present invention is to provide a kind of complete circulation preparation method who produces LiFePO 4 take the lithium ore deposit as the lithium source, complete circulation preparation method of the present invention need not to carry out that numerous and diverse lithium salts is refining, purification process, and part has been omitted sulfuric acid process and prepared crystallisation by cooling, separation, removal of impurities, drying and other steps in the lithium salts; And, the water of condensation byproduct that produces in the preparation lithium source procedure is cycled to used in preparation ferrous salt solution or phosphorus source solution, and the lithium byproduct that contains in the LiFePO 4 production is cycled to used in again the process that the lithium ore deposit prepares the lithium source, and byproduct is turned waste into wealth, realize recycling economy, not only saved cost but also environmental protection.
Technical scheme of the present invention is specifically passed through following steps:
(1) with the calcining of lithium ore deposit, acidifying, leaching, purification, separation, the filtrate evaporation concentration makes primary lithium liquid;
(2) primary lithium liquid is transformed freezing, filter, washing, the filtrate evaporation concentration makes reaction lithium liquid;
(3) will react with lithium liquid and ferrous salt solution, phosphorus source solution and carry out after the liquid phase building-up reactions obtains LiFePO 4, filter, washing, to filter cake washing liquid, do not detect lithium ion, in filter cake, add an amount of water, it is diluted to mud, add the glycogen material, calcining namely gets the ferrousphosphate lithium material that carbon coats;
Wherein, the condensate water circulatory that produces in step (1) and the described evaporating concentration process of step (2) is used at least a of preparation phosphorus source solution, ferrous salt solution; Collect filtrate and filter cake washing liquid in the step (3), namely contain the solution of lithium salts or reclaim filtrate, it is returned the leaching operation of step (1), in addition recycle;
Step (2) described " transforming freezing " refers to add sodium salt in the primary lithium liquid Li in the primary lithium liquid 2SO 4With the sodium salt reaction, produce another kind of lithium salts and Na 2SO 4, again with the cooling of gained reaction soln, thereby so that the sulfate crystal that generates is separated out, filtering separation is removed.
In the preferred technical solution of the present invention, described lithium ore deposit is selected from any or its combination of triphane, amblygonite, montebrasite, lithionite, petalite.
In the preferred technical solution of the present invention, the described reaction of step (2) is preferably 26.2g/L with the lithium content 25～27g/L in the lithium liquid.
In the preferred technical solution of the present invention, the Ca of the described reaction of step (2) in the lithium liquid 2+, Mg 2+, Cl -, K +, Cu 2+, Pb 2+Any content be not higher than 0.01%.
In the preferred technical solution of the present invention, Fe in the described ferrous salt solution 2+Concentration is 54-59g/L, is preferably 55.8g/L.
In the preferred technical solution of the present invention, PO in the solution of described phosphorus source 4 3-Concentration is 680～800g/L, is preferably 719.2g/L.
In the preferred technical solution of the present invention, the volume ratio that participates between liquid reactive lithium solution, ferrous salt solution, the phosphorus source solution is 2.5～3.5: 3～4: 0.3～0.7, and preferred volume ratio is 3: 3.5: 0.5.
In the preferred technical solution of the present invention, in step (3), will evenly mix with lithium solution, ferrous salt solution and phosphorus source solution for the metal salt solution that mixes, carry out the liquid phase building-up reactions.
In the preferred technical solution of the present invention, the metal salt solution that be used for to mix is selected from any or its combination of the metal salt solution of Co, Ni, Al, Zr.
In the preferred technical solution of the present invention, the ferrous salt raw material of preparing described ferrous salt solution is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate.
In the preferred technical solution of the present invention, the phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
Step (2) transforms when freezing, and the sodium salt that adds in the primary lithium liquid is selected from any or its combination in yellow soda ash, sodium hydroxide, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, sodium-chlor, sodium oxalate, the SODIUMNITRATE; Be preferably any or its combination in sodium-chlor, the sodium hydroxide.Correspondingly, the another kind of lithium salts that generates is any or its combination in Quilonum Retard, lithium hydroxide, monometallic, Trilithium phosphate, lithium chloride, lithium oxalate, the lithium nitrate.In the preferred technical solution of the present invention, the described glycogen material of step (3) is selected from any or its combination of sucrose, glucose, lactose.
In the preferred technical solution of the present invention, filtrate in the step (3) is namely contained the solution of lithium salts, and the solution that contains lithium salts is selected from any or its combination in lithium sulfate solution, Quilonum Retard solution, lithium hydroxide solution, monometallic solution, Trilithium phosphate solution, lithium chloride solution, lithium oxalate solution, the lithium nitrate solution.
In the preferred technical solution of the present invention, the preparation process of primary lithium liquid comprises the steps:
After A, lithium ore deposit place 1100～1380 ℃ of lower calcinings, in the lithium ore deposit, be to add sulfuric acid in the lithium ore deposit of 1: 4～7 (w/w) after calcining to carry out acidification by acid material ratio; In the lithium ore deposit, be 2-3 by liquid-solid ratio: 1 (w/w) adds entry or reclaims filtrate in acidification liquid, regulate pH value to 5.7～6.2, leaves standstill, and filters, and gets mother liquor 1;
B, adjusting mother liquor 1pH 8.5～9.7 leave standstill, and filter, and get mother liquor 2;
C, adjusting mother liquor 2pH 10～10.8 leave standstill, and filter, and get mother liquor 3;
Ca in D, the detection mother liquor 3 2+Concentration adds equimolar Na 2CO 3, stir, leave standstill, filter, get mother liquor 4;
E, evaporation concentration mother liquor 4 are to its Li +Concentration is 65～75g/L, filters, and gets mother liquor 5, and wherein, the water of condensation that produces in the evaporating concentration process is used for any or its combination of preparation ferrous salt solution, phosphorus source solution.
In the preferred technical solution of the present invention, reaction comprises the steps: with the preparation process of lithium liquid
SO in a, the detection mother liquor 5 4 2-Concentration adds an amount of sodium salt, with the SO in the mother liquor 5 4 2-All change into Na 2SO 4Stir, crystallisation by cooling, filter, mother liquor 6, wherein, described sodium salt is selected from any or its combination in yellow soda ash, sodium-chlor, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, sodium hydroxide, sodium oxalate, the SODIUMNITRATE, be preferably any or its combination in sodium-chlor, the sodium hydroxide, preferred cooling temperature is-15 ℃～0 ℃;
B, evaporation concentration mother liquor 6, containing the lithium amount to it is 25-27g/L, preferably its to contain the lithium amount be 26.2g/L, must react and use lithium solution, wherein, the water of condensation that produces in the evaporating concentration process is used for any or its combination of preparation ferrous salt solution, phosphorus source solution.
In the preferred technical solution of the present invention, described liquid phase synthesis condition is that reaction lithium solution, ferrous salt solution, phosphorus source solution adding reactor with the reaction aequum are heated to 150～220 ℃, be incubated 220～720 minutes, after the cooling, filter, get filter cake, for subsequent use, simultaneously, the filtrate of collecting is returned the leaching operation of primary lithium liquid, in addition recycle.
In the preferred technical solution of the present invention, washing described in the step (3) refers to wash to filter cake washing liquid and do not detect lithium ion, gets filter cake, and is for subsequent use, simultaneously, filtrate returned the leaching operation of primary lithium liquid, in addition recycle.
" not detecting lithium ion in the filter cake washing liquid " of the present invention refers to that the lithium ion content in the filter cake washing liquid is not higher than 0.01%.
In the preferred technical solution of the present invention, in the step (3) in cleaning filter cake the add-on of glycogen material be preferably 10wt% for cleaning 5～20wt% of filter cake solid content.
In the preferred technical solution of the present invention, calcining is under the provide protection of protective gas described in the step (3), and the even hybrid dry matter of calcining glycogen material and filter cake under 650～1000 ℃ of conditions is to make the LiFePO 4 of carbon coating.
In the preferred technical solution of the present invention, protective gas of the present invention is selected from any or its combination of argon gas, nitrogen, hydrogen.
In the preferred technical solution of the present invention, the preparation process of mother liquor 1 comprises the steps: to calcine the lithium ore deposits 50～300 minutes under 1100～1380 ℃, cooling, levigate, in the lithium ore deposit, carried out acidification 50-200 minute than adding sulfuric acid in the lithium ore deposit of 1: 4～7 (w/w) after calcining by the acid material; In the lithium ore deposit, be that 2～3: 1 (w/w) adds water or reclaim filtrate by liquid-solid ratio, regulate pH value to 5.7～6.2, stirred 35～50 minutes, leave standstill, filter, collect filtrate, namely get mother liquor 1.
In the preferred technical solution of the present invention, the calcination time under the provide protection of protective gas is 3～15 hours.
In the preferred technical solution of the present invention, the material of regulating pH is selected from any or its combination of sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, is preferably any or its combination of sodium hydroxide, yellow soda ash.
In the preferred technical solution of the present invention, described liquid phase building-up reactions is carried out in confined conditions, effectively to prevent Fe 2+Oxidation.
Another object of the present invention is to provide a kind of LiFePO 4 of carbon coating, complete preparation method prepares by circulation of the present invention.
In the preferred technical solution of the present invention, the purity of the LiFePO 4 that described carbon coats is not less than 99.97%, and preferred 1C specific storage is not less than 141mAh/g, more preferably Ca in the LiFePO 4 of carbon coating 2+, Mg 2+, SO4 2-, Cl -, Na +, K +, Cu 2+, Pb 2+Any content is not higher than 0.01%.
The LiFePO 4 that the carbon that another object of the present invention is to that the present invention is made coats is preferred for preparing the application in the lithium-ion-power cell material for the preparation of the application in the lithium ion battery material.
In order clearly to explain protection scope of the present invention, the present invention carries out description below to following term:
" primary lithium liquid " of the present invention refer to by produce in the lithium ore deposit through rough purification, separate the lithium solution make.
" reaction lithium liquid " of the present invention claims again " building-up reactions lithium liquid ", " reaction order lithium liquid ", refers to be directly used in the lithium solution that participates in the liquid phase building-up reactions.
" reclaim filtrate " of the present invention refers to the filtrate of collecting in the LiFePO 4 liquid phase building-up process, the wash filtrate of perhaps collecting in the LiFePO 4 filter cake washing process, " the reclaiming filtrate " of collecting can be returned the leaching operation of primary lithium liquid, in addition recycle.
" the even hybrid dry matter of glycogen material and filter cake " of the present invention refers to add an amount of water in the LiFePO 4 filter cake after cleaning, it is diluted to mud, the glycogen material that adds again filter cake solid content 5～20wt.%, after evenly mixing, dry, the even drying composite of gained, wherein, the add-on of preferred glycogen material is 10wt.%.
" solution that contains lithium salts " of the present invention refers to the lithium salt solution that generates in the LiFePO 4 production process, wherein, described lithium salt solution is selected from any or its combination of lithium sulfate solution, Quilonum Retard solution, lithium hydroxide solution, monometallic solution, Trilithium phosphate solution, lithium chloride solution, lithium oxalate solution, lithium nitrate solution.
" transforming freezing " described in the step of the present invention (2) refers to add sodium salt in primary lithium liquid, makes the Li in the primary lithium liquid 2SO 4With the sodium salt reaction, produce another kind of lithium salts and Na 2SO 4Again the gained reaction soln is cooled off, thereby so that the sulfate crystal that generates is separated out, be isolated by filtration and remove, must contain lithium mother liquor (being mother liquor 6), wherein, described sodium salt is selected from any or its combination in yellow soda ash, sodium hydroxide, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, sodium-chlor, sodium oxalate, the SODIUMNITRATE, is preferably any or its combination in sodium-chlor, the sodium hydroxide; Described another kind of lithium salts comprises any or its combination in Quilonum Retard, lithium hydroxide, monometallic, Trilithium phosphate, lithium chloride, lithium oxalate, the lithium nitrate.
Except as otherwise noted, per-cent of the present invention is weight percentage.
The method for detecting purity of LiFePO 4 of the present invention is that X-ray diffraction analysis method and chemical composition analysis method combine, wherein, is the X-ray diffraction analysis method selected from instrument Information Network " XRD powder X-ray X-ray analysis X method ", http://www.instrument.com.cn/download/DownLoadFile.asp? id=1673 48﹠amp; Huodong=3; The chemical analysis method of LiFePO 4 is selected from Chinese Industrial Standards (CIS) quality net,
http://hi.baidu.com/795007/blog/item/018fbcd3132e5531970a16ac.html)。
Measuring method and the Ca of 1C specific storage of the present invention (mAh/g) 2+, Mg 2+, Cl -, Na +, K +, Cu 2+, Pb 2+The detection method of equal size is selected from 863 Modern Transportation Technology field offices of Department of Science and Technology issue on March 31st, 2010 " lithium ion power storage battery critical material performance test standard ",
http://doc.mbalib.com/view/2679ed041aa01e1ad4401643428c6f43.html)。
Wherein, the measuring method of 1C specific storage is as follows:
Positive electrode material: conductive agent (SP): PVDF (HSV900)=83: 10: 7; Negative pole: metal Li; Electrolytic solution: 1.1MLiPF6, EC: DEC: DMC=1: 1: 1; Barrier film: Celgard 2325 forms button cell (2430).
Under 25 ℃ ± 2 ℃ conditions, half-cell, then extremely discharges by voltage (2.0V) with the 1C constant current discharge to charging by voltage (3.9V) with the 1C constant current charge, circulates 3 times.Specific storage according to the mean value calculation positive electrode material of three loading capacities.5 in parallel testing half-cell sample after the removal outlier, is averaged.
C=C on average discharges/[(M electrode-M aluminium foil) * 0.83]
C wherein: the specific storage mAh/g of positive electrode material; C on average discharges: the mean value mAh of three loading capacities of half-cell; M electrode: the quality g of positive plate; M aluminium foil: the quality g of aluminium foil.
The present invention uses other pH value Auto-regulators (such as any or its combination in sodium hydroxide, potassium hydroxide, yellow soda ash, the salt of wormwood) instead and replaces CaCO 3, avoid in reaction system, bringing into a large amount of Ca 2+, and adopt classification to regulate the pH value and carry out classification and staticly settle, can effectively remove Ca 2+, Mg 2+, SO4 2-Deng.
The present invention is with the Ca in the yellow soda ash precipitation solution 2+, Mg 2+Deng impurity, it is thoroughly removed by filter, make reaction lithium solution.
The present invention reacts with lithium concentration and foreign matter content thereof in the lithium solution by rationally control, and form needs according to the preparation of LiFePO 4, with reaction with organically mating between the phosphoric acid solution concentration of the lithium concentration in the lithium solution and participation liquid phase building-up reactions, the ferrous iron solution concentration, can effectively reduce take the lithium ore deposit as lithium source preparation feedback with the purifying in the lithium solution process, make with extra care and production cost that evaporation concentration is increased.
The present invention take the lithium ore deposit as the lithium source for the production of the complete circulation preparation method of LiFePO 4, the reaction that need not to make is carried out numerous and diverse refining, purification process with lithium liquid, part has been omitted sulfuric acid process and has been prepared crystallisation by cooling, separation, removal of impurities, drying and other steps in the lithium salts, and shortened evaporation concentration time of mother liquor, saved the cost of marketing of lithium salts, and, the water of condensation byproduct that produces in the preparation lithium source procedure is cycled to used in preparation ferrous salt solution or phosphorus source solution, and the lithium byproduct that contains in the LiFePO 4 production is cycled to used in again the process that the lithium ore deposit prepares the lithium source.Therefore, it is short that circulation technology of the present invention has technical process, energy consumption is low, comprehensive benefit is high, realize the advantages such as recycling economy, not only can reduce production costs significantly, improved the utilization ratio of resource, realize recycling economy, and form needs according to the preparation of LiFePO 4, lithium concentration or its foreign matter content of control reaction in the lithium solution, with the phosphoric acid solution concentration of reaction with the lithium concentration in the lithium solution and participation liquid phase building-up reactions, organically mate between the ferrous iron solution concentration, and it is high that the LiFePO 4 of preparation gained has purity, chemical property is excellent, stability, the advantages such as high conformity, the 1C loading capacity can reach more than the 140mAh/g.
Specify the present invention below with reference to embodiment, embodiments of the invention only are used for technical scheme of the present invention is described, and non-limiting essence of the present invention.
Embodiment 1The preparation of LiFePO 4
(1) takes by weighing the 50kg triphane, 1100 ℃ of lower calcinings 50 minutes, cooling, levigate, adding 7.1kg sulfuric acid (the acid material was than 1: 7) processed 50 minutes, under agitation condition, the triphane powder that is added with sulfuric acid is poured in 114kg (liquid-solid ratio 2: the 1) water, regulate pH value to 5.7 with NaOH, stirred 35 minutes, leave standstill, filter, get mother liquor 1;
(2) regulate mother liquor 1pH value to 8.5 with NaOH, stirring reaction 5 minutes leaves standstill, and filters, and gets mother liquor 2; Regulate the pH value to 10.8 of mother liquor 2 with NaOH, stirring reaction 5 minutes leaves standstill again, and filters, and gets mother liquor 3; In mother liquor 3, add 236.6 gram Na 2CO 3, stirring reaction 30 minutes leaves standstill, and filters, and gets mother liquor 4;
(3) the evaporation concentration mother liquor 4, to its lithium content be 65g/L, leave standstill, filter, get mother liquor 5, wherein, the water of condensation of evaporation concentration gained is used for preparation ferrous salt solution or phosphorus source solution;
(4) add 5.46kg NaOH in mother liquor 5, stir, be cooled to-15-0 ℃, crystallization is filtered, and gets mother liquor 6;
(5) the evaporation concentration mother liquor 6, to its lithium content 25.34g/L, must react and use lithium solution, and wherein, the water of condensation of evaporation concentration gained is used for preparation ferrous salt solution or phosphorus source solution;
(6) taking by weighing 5531.0 gram content is 62.0% iron protochloride, adds water, and it is mixed with 36 liters of (Fe of ferrous salt solution 2+Concentration: 58.3g/L);
(7) take by weighing 14071.6 grams, 98.0% 3 water ammonium phosphate, add water, it is mixed with 5 liters of (PO of phosphorus source solution 4 3-Concentration: 685.9g/L);
(8) measure 3 liters of lithium solution, 3.5 liters of ferrous salt solutions and 0.5 liter of phosphorus source solution, under whipped state, add reactor, continue to stir, be heated to 150 ℃, be incubated 720 minutes, after the cooling, emit filtration, filter cake, and collect filtrate, will collect filtrate and return in addition recycle of step (1);
(9) washing leaching cake is 2 times, until do not detect lithium ion in the filter cake washing liquid, gets filter cake, and collects filtrate, will collect filtrate and return in addition recycle of step (1); Add an amount of water in filter cake, it is diluted to mud, add 27.5 gram sucrose (5%) again, mix, drying gets the even hybrid dry matter of glycogen material and filter cake;
(10) under argon shield, the even hybrid dry matter of glycogen material and filter cake was calcined 12 hours under 650 ℃, namely get the LiFePO 4 that carbon coats.
According to measuring method of the present invention, the purity that records the carbon coating minute LiFePO 4 of embodiment 1 preparation gained is that 99.99%, 1C specific storage (mAh/g) is 141mAh/g, and its Ca 2+, Mg 2+, SO4 2-, Cl -, Na +, K +, Cu 2+, Pb 2+Any content is not higher than 0.01%.
Table 1 different lithium source produces the needed lithium raw materials cost of LiFePO 4 that 1 ton of carbon coats
Figure BDA0000100532410000121
Illustrate: "---" expression nothing in the table 1, "+" expression cost increases, and the described lithium of described " lithium raw materials cost " table 1 of serving as reasons source begins to obtain reacting the cost of using lithium liquid.
By as seen from Table 1, compare with the method for the LiFePO 4 for preparing the carbon coating take lithium salts as the lithium source, the present invention has very significantly cost advantage take the lithium ore deposit as the lithium source for the preparation of LiFePO 4, and its comprehensive cost can be saved more than 12,000 yuan/tons.
Embodiment 2The preparation of LiFePO 4
(1) takes by weighing the 50kg amblygonite, 1380 ℃ of lower calcinings 300 minutes, cooling, levigate, adding 12.5kg sulfuric acid (expecting than 1: 4 by acid) processed 200 minutes, under agitation condition, pour the triphane powder that is added with acid into 187.5kg and reclaim in the filtrate (liquid-solid ratio 3: 1), regulate pH value to 6.2 with NaOH, stirred 50 minutes, leave standstill, filter, get mother liquor 1;
(2) regulate mother liquor 1pH value to 9.7 with NaOH, stirring reaction 12 minutes leaves standstill, and filters, and gets mother liquor 2; Regulate the pH value to 10 of mother liquor 2 with NaOH, stirring reaction 12 minutes leaves standstill again, and filters, and gets mother liquor 3; In mother liquor 3, add 240.5 gram Na 2CO 3, stirring reaction 10 minutes leaves standstill, and filters, and gets mother liquor 4;
(3) the evaporation concentration mother liquor 4, to its lithium content be 75g/L, leave standstill, filter, get mother liquor 5, wherein, the water of condensation of evaporation concentration gained is used for preparation ferrous salt solution or phosphorus source solution;
(4) add 5.45kgNaOH in mother liquor 5, stir, be cooled to 0 ℃, crystallization is filtered, and gets mother liquor 6;
(5) the evaporation concentration mother liquor 6, to its lithium content 26.95g/L, must react and use lithium solution, and wherein, the water of condensation of evaporation concentration gained is used for preparation ferrous salt solution or phosphorus source solution;
(6) taking by weighing 3568.6 gram content is 98.3% ferrous sulfate, adds water, and it is mixed with 35 liters of (Fe of ferrous iron solution 2+Concentration is 54.8g/L);
(7) taking by weighing 4825.3 gram content is 85.3% phosphoric acid, adds water, and it is mixed with 5 liters of (PO of preparation phosphorus source solution 4 3-Concentration is 798.0g/L);
(8) measure 3 liters of lithium solution, 3.5 liters of ferrous salt solutions and 0.5 liter of phosphorus source solution, under agitation condition, it is added reactor, continue to stir, be heated to 220 ℃, be incubated 220 minutes, after the cooling, leave standstill, filter, filter cake, will collect the leaching operation that filtrate is returned step (1), in addition recycle;
(9) washing leaching cake is 5 times, until do not detect lithium ion in the filter cake washing liquid, gets filter cake, will collect the leaching operation that filtrate is returned step (1), in addition recycle; Add an amount of water in filter cake, it is diluted to mud, add 110 gram glucose (20%) again, mix, drying gets the even hybrid dry matter of glycogen material and filter cake;
(10) under nitrogen protection, the even hybrid dry matter of glycogen material and filter cake was calcined 3 hours under 650 ℃, namely get the LiFePO 4 product that carbon coats, its X ray diffracting spectrum is seen Fig. 3.
According to measuring method of the present invention, the purity that records the LiFePO 4 that the carbon of embodiment 2 preparation gained coats is that 99.98%, 1C specific storage (mAh/g) is 140mAh/g, and Ca in the LiFePO 4 2+, Mg 2+, SO4 2-, C1 -, Na +, K +, Cu 2+, Pb 2+Any content is not higher than 0.01%.
Embodiment 3-9The preparation of LiFePO 4
The preparation technology of embodiment 3-9 is with embodiment 1, and required raw materials and processing parameter see Table 2.Simultaneously, will " corresponding lithium salts is made first according to sulfuric acid process in described lithium ore deposit; then adding deionized water makes the lithium solution that concentration is 25-27g/L; and all the other steps of its preparation LiFePO 4 are with (6)～(10) of embodiment 1; but the preparation method of filtrate and water of condensation is reclaimed in not recycle " and as a comparison case, and the production cost that Comparative Examples and embodiment 3-9 prepare the LiFePO 4 of gained compared, the results are shown in Table 2.
Raw materials and the processing parameter of table 2 embodiment 3-9
By as seen from Table 2, detect according to measuring method of the present invention, the purity that embodiment 3-9 prepares the gained LiFePO 4 is not less than 99.97%, and Ca in the LiFePO 4 2+, Mg 2+, SO4 2-, Cl -, Na +, K +, Cu 2+, Pb 2+Any content is not higher than 0.01%, 1C specific storage and reaches more than the 140mAh/g.
To sum up, the LiFePO 4 that the complete circulation technology of the present invention prepares gained has that purity is high, chemical property is excellent, the advantages such as stability and high conformity.
And, with Comparative Examples (be about to described lithium ore deposit according to sulfuric acid process first refining purifying be dried to corresponding lithium salts, add deionized water, being made into concentration is the lithium solution of 25-27g/L, all the other preparation processes are with (6)-(10) of embodiment 1, but the preparation method of filtrate and water of condensation is reclaimed in not recycle) compare, the complete circulation technology of the present invention can be according to the preparation needs of LiFePO 4, lithium concentration or its foreign matter content of control reaction in the lithium solution, part has been omitted the crystallisation by cooling that sulfuric acid process prepares the lithium salts process, the operations such as separation and drying, and shortened evaporation concentration time of mother liquor, saved the cost of marketing of lithium salts, reduce the difficulty of the refining clarification of lithium salts, significantly reduce production costs; Simultaneously, recycle water of condensation and reclaim filtrate has reduced the cost of preparation deionized water or distilled water, has saved the processing cost of the waste water in the cost recovery, particularly filtrate of filtrate, and its comprehensive cost can be saved more than 12000 yuan/tons.

Claims (41)

1. a complete circulation preparation method who produces LiFePO 4 take the lithium ore deposit as the lithium source comprises the steps:
(1) with the calcining of lithium ore deposit, acidifying, leaching, purification, separation, the filtrate evaporation concentration makes primary lithium liquid;
(2) primary lithium liquid is transformed freezing, filter, washing, the filtrate evaporation concentration makes reaction and use lithium liquid, wherein, lithium content 25～27 g/Ls of reaction in the lithium liquid;
(3) will react with lithium liquid and ferrous salt solution, phosphorus source solution and carry out after the liquid phase building-up reactions obtains LiFePO 4, filter, washing, to filter cake washing liquid, do not detect lithium ion, in filter cake, add an amount of water, it is diluted to mud, add the glycogen material, drying, calcining namely gets the ferrousphosphate lithium material that carbon coats; Described calcining is under the protection of protective gas, under 650～1000 ℃ of conditions even hybrid dry matter 4-15 hour of calcining glycogen material and filter cake;
Wherein, the condensate water circulatory that produces in step (1) and the described evaporating concentration process of step (2) is used at least a of preparation phosphorus source solution, ferrous salt solution; Collect filtrate and filter cake washing liquid in the step (3), namely contain the solution of lithium salts or reclaim filtrate, it is returned the leaching operation of step (1), in addition recycle;
Step (2) described " transforming freezing " refers to add sodium salt in the primary lithium liquid Li in the primary lithium liquid 2SO 4With the sodium salt reaction, produce another kind of lithium salts and Na 2SO 4, the solution cooling so that the sulfate crystal that generates is separated out, is removed by solid-liquid separation.
2. preparation method according to claim 1 is characterized in that: the described lithium of step (1) ore deposit is selected from any or its combination of triphane, amblygonite, montebrasite, lithionite, petalite.
3. preparation method according to claim 2, it is characterized in that: the described reaction of step (2) is 25～27 g/L with the lithium content in the lithium liquid; Fe in the described ferrous salt solution 2+Concentration is 54～59g/L; PO in the solution of described phosphorus source 4 3-Concentration is 680～780g/L; The volume ratio that participates between liquid reactive lithium solution, ferrous salt solution, the phosphorus source solution is 2.5～3.5 ︰ 3-4 ︰ 0.3～0.7.
4. preparation method according to claim 3, it is characterized in that: the described reaction of step (2) is 26.2g/L with the lithium content in the lithium liquid; Fe in the described ferrous salt solution 2+Concentration is 55.8g/L; PO in the solution of described phosphorus source 4 3-Concentration is 719.2g/L; The volume ratio that participates between liquid reactive lithium solution, ferrous salt solution, the phosphorus source solution is 3 ︰, 3.5 ︰ 0.5.
5. preparation method according to claim 1, it is characterized in that: step (2) transforms when freezing, and the sodium salt that adds in the primary lithium liquid is selected from any or its combination in yellow soda ash, sodium-chlor, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, sodium hydroxide, sodium oxalate, the SODIUMNITRATE.
6. preparation method according to claim 5 is characterized in that: step (2) transforms when freezing, and the sodium salt that adds in the primary lithium liquid is selected from any or its combination in sodium-chlor, the sodium hydroxide.
7. each described preparation method according to claim 1-6 is characterized in that: the described glycogen material of step (3) is selected from any or its combination of sucrose, glucose, lactose.
8. preparation method according to claim 7 is characterized in that: the add-on of described glycogen material is for cleaning the 5-20wt% of filter cake solid content.
9. preparation method according to claim 8 is characterized in that: the add-on of described glycogen material is for cleaning 10 wt% of filter cake solid content.
10. each described preparation method according to claim 1-6, it is characterized in that: the filtrate in the step (3) is namely contained the solution of lithium salts, and the described solution that contains lithium salts is selected from any or its combination in lithium sulfate solution, Quilonum Retard solution, lithium hydroxide solution, monometallic solution, Trilithium phosphate solution, lithium chloride solution, lithium oxalate solution, the lithium nitrate solution.
11. preparation method according to claim 7, it is characterized in that: the filtrate in the step (3) is namely contained the solution of lithium salts, and the described solution that contains lithium salts is selected from any or its combination in lithium sulfate solution, Quilonum Retard solution, lithium hydroxide solution, monometallic solution, Trilithium phosphate solution, lithium chloride solution, lithium oxalate solution, the lithium nitrate solution.
12. preparation method according to claim 8, it is characterized in that: the filtrate in the step (3) is namely contained the solution of lithium salts, and the described solution that contains lithium salts is selected from any or its combination in lithium sulfate solution, Quilonum Retard solution, lithium hydroxide solution, monometallic solution, Trilithium phosphate solution, lithium chloride solution, lithium oxalate solution, the lithium nitrate solution.
13. preparation method according to claim 9, it is characterized in that: the filtrate in the step (3) is namely contained the solution of lithium salts, and the described solution that contains lithium salts is selected from any or its combination in lithium sulfate solution, Quilonum Retard solution, lithium hydroxide solution, monometallic solution, Trilithium phosphate solution, lithium chloride solution, lithium oxalate solution, the lithium nitrate solution.
14. each described preparation method according to claim 1～6 is characterized in that: the ferrous raw material of the described ferrous salt solution of preparation is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate in the step (3); The phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
15. preparation method according to claim 7 is characterized in that: the ferrous raw material of the described ferrous salt solution of preparation is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate in the step (3); The phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
16. preparation method according to claim 8 is characterized in that: the ferrous raw material of the described ferrous salt solution of preparation is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate in the step (3); The phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
17. preparation method according to claim 9 is characterized in that: the ferrous raw material of the described ferrous salt solution of preparation is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate in the step (3); The phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
18. preparation method according to claim 10 is characterized in that: the ferrous raw material of the described ferrous salt solution of preparation is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate in the step (3); The phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
19. preparation method according to claim 11 is characterized in that: the ferrous raw material of the described ferrous salt solution of preparation is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate in the step (3); The phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
20. preparation method according to claim 12 is characterized in that: the ferrous raw material of the described ferrous salt solution of preparation is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate in the step (3); The phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
21. preparation method according to claim 13 is characterized in that: the ferrous raw material of the described ferrous salt solution of preparation is selected from any or its combination of ferrous bromide, iron protochloride, ferrous sulfate, ferrous perchlorate, Iron nitrate in the step (3); The phosphorus source raw material of preparing described phosphorus source solution is selected from any or its combination of ammonium phosphate, phosphoric acid, Trilithium phosphate, primary ammonium phosphate.
22. each described preparation method according to claim 1～6 is characterized in that: the preparation process of primary lithium liquid is through following step:
After A, lithium ore deposit place 1100-1380 ℃ of lower calcining, in the lithium ore deposit, in acid material w/w than being that adding sulfuric acid carries out acidification in the lithium ore deposit of ratio after calcining of 1 ︰ 4～7; Then in the lithium ore deposit, be that the ratio of 2～3 ︰ 1 adds entry or reclaims filtrate in liquid-solid ratio w/w in acidification liquid, regulate pH value to 5.7～6.2, leave standstill, filter, get mother liquor 1;
The pH of B, adjusting mother liquor 1 is 8.5～9.7, leaves standstill, and filters, and gets mother liquor 2;
The pH of C, adjusting mother liquor 2 is 10～10.8, leaves standstill, and filters, and gets mother liquor 3;
Ca in D, the detection mother liquor 3 2+Concentration adds equimolar Na 2CO 3, stir, leave standstill, filter, get mother liquor 4;
E, evaporation concentration mother liquor 4 are to its Li +Concentration is 65-75g/L, filters, and gets mother liquor 5, and wherein, the water of condensation that produces in the evaporating concentration process is used for any or its combination of preparation ferrous salt solution, phosphorus source solution;
Wherein the described recovery of steps A filtrate is filtrate or the filter cake washing liquid in the step (3).
23. preparation method according to claim 22, the preparation method of described mother liquor 1, the following step of process: calcining lithium ore deposits are 50～300 minutes under 1100～1380 ℃, cooling, levigate, in the lithium ore deposit, carried out acidification 50-200 minute than adding sulfuric acid in the lithium ore deposit of w/w1 ︰ 4～7 after calcining by the acid material; In the lithium ore deposit, be that 2～3 ︰ 1 add water or reclaim filtrate by liquid-solid ratio w/w, regulate pH value to 5.7～6.2, stirred 35～50 minutes, leave standstill, filter, collect filtrate, namely get mother liquor 1.
24. preparation method according to claim 22 is characterized in that: regulate any or its combination that pH selects sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood.
25. preparation method according to claim 24 is characterized in that: regulate any or its combination that pH selects sodium hydroxide, yellow soda ash.
26. preparation method according to claim 23 is characterized in that: regulate any or its combination that pH selects sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood.
27. preparation method according to claim 26 is characterized in that: regulate any or its combination that pH selects sodium hydroxide, yellow soda ash.
28. preparation method according to claim 22 is characterized in that: step (2) the reaction following step of preparation process process of lithium liquid:
SO in a, the detection mother liquor 5 4 2-Concentration adds sodium salt, with the SO in the mother liquor 5 4 2-All change into Na 2SO 4, stir, cooling, crystallization is filtered, and gets mother liquor 6, and wherein, described sodium salt is selected from any one or two kinds of in yellow soda ash, sodium-chlor, SODIUM PHOSPHATE, MONOBASIC, sodium phosphate, sodium hydroxide, sodium oxalate, the SODIUMNITRATE;
B, evaporation concentration mother liquor 6, containing the lithium amount to it is 25～27 g/L, must react and use lithium solution;
Wherein, the water of condensation that produces in the evaporating concentration process is used for any or combination of preparation ferrous salt solution, phosphorus source solution.
29. preparation method according to claim 28 is characterized in that: the described sodium salt of a step is selected from any or its combination in sodium-chlor, the sodium hydroxide.
30. preparation method according to claim 28 is characterized in that: the described cooling temperature of a step is-15 ℃～0 ℃.
31. preparation method according to claim 28 is characterized in that: b step evaporation concentration mother liquor 6, containing the lithium amount to it is 26.2g/L.
32. each described preparation method according to claim 1～6, it is characterized in that: the described liquid phase synthesis condition of step (3) is, the reaction of reaction aequum is added reactor with lithium solution, ferrous salt solution, phosphorus source solution, be heated to 150～220 ℃, be incubated 220～720 minutes, after the cooling, filter, get filter cake, be used for calcination reaction; Collect filtrate, filtrate is returned the leaching operation of step (1), in addition recycle.
33. preparation method according to claim 1 is characterized in that: the described protective gas of step (3) is selected from any or its combination of argon gas, nitrogen, hydrogen.
34. preparation method according to claim 1 is characterized in that: the described liquid phase building-up reactions of step (3) is carried out in confined conditions.
35. preparation method according to claim 1, it is characterized in that: in step (3), add the metal salt solution that is used for doping, to carry out described liquid phase building-up reactions with lithium solution, ferrous salt solution and phosphorus source solution for the metal salt solution that mixes, wherein, described metal salt solution for mixing is selected from any or its combination of the metal salt solution of Co, Ni, Al, Zr.
36. the LiFePO 4 that carbon coats, each described preparation method prepares by claim 1～35.
37. LiFePO 4 according to claim 36 is characterized in that: the purity of described LiFePO 4 is not less than 99.97%.
38. described LiFePO 4 according to claim 37, it is characterized in that: the 1C specific storage of described LiFePO 4 is not less than 141 mAh/g.
39. described LiFePO 4 is characterized in that: the Ca in the LiFePO 4 according to claim 38 2+, Mg 2+, SO4 2-, Cl -, Na +, K +, Cu 2+, Pb 2+Any content is not higher than 0.01%.
40. the LiFePO 4 that each described carbon of claim 36-39 coats is for the preparation of the application in the lithium ion battery material.
41. according to claim 40 described application is characterized in that: the LiFePO 4 that described carbon coats is for the preparation of the lithium-ion-power cell material.
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