Abstract:
A method of synthesizing LiFePO 4  compounds and analogs thereof for use in secondary electrodes involves mixing the starting materials and polymerizing the mixture into a gel. The gel form allows thorough milling and mixing of the reagents and results in a smaller and more uniform particle size in the resultant electrode formed and a well crystallized structure based on the X-ray diffraction pattern.

Description:
CLAIM OF PRIORITY 
       [0001]    This application claims priority to U.S. Provisional Patent Application No. 61/224,796 entitled “METHOD OF SOLID-LIQUID MIXING GEL PROCESS FOR LiFePO 4  SYNTHESIS” by Inventors Ning Wang and Shifan Cheng, filed Jul. 10, 2009, the contents of which are incorporated herein by reference. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The present invention relates to a processing method for cathode material of the secondary (rechargeable) lithium battery. More specifically, the invention relates to a processing method for LiFePO 4  and similar secondary battery electrode materials. The invention provides a gel processing method or polymerization method for mixing the solid reactants and liquid reactants. Finally, the reactants are evenly distributed in the 3-dimension gel structure. 
       BACKGROUND OF THE INVENTION 
       [0003]    Portable electronic devices, such as notebook computers, mobile phones, and the like, become more and more popular. At the same time portable devices, such as electric tools, require more powerful energy sources. Currently, a clean energy source has become more and more significant for a battery powered vehicle application. Secondary (rechargeable) batteries play a very important role for all of the above applications. Cobalt-based lithium batteries have been extensively used for over 10 years. The low thermal stability of cobalt-based lithium battery is a critical factor to constrain its further application, especially for high power application. John Goodenough et al. invented a new lithium compound, LiFePO 4  for use as a cathode material, which is much more stable than cobalt-based lithium compounds (U.S. Pat. No. 5,910,382). 
         [0004]    LiFePO 4  may be synthesized by different routes. The related methods may be divided into two main groups: solid processes (including processes involving a slurry with solid powders) and liquid processes. A typical solid process is represented by a published patent application of A123 Systems (see U.S. 2007/0190418). The raw materials required for the synthesis are Li 2 CO 3 , iron oxalate and ammonium phosphate. These powders are fully milled, then fired at 700° C. for 5 h. The specific surface is 45.4 m 2 /g, corresponding to an equivalent spherical particle diameter of 37.7 nm. This nano powder shows an outstanding capacity at higher C-rate. At a 5C rate, the capacity retention was 95%, at a 10C rate, the capacity retention was about 90%. A carbon thermal reaction was combined with the powder processing method (see U.S. Pat. Nos. 6,528,033; 6,716,372; 7,060,206; and 7,348,100). The available raw materials include carbon and FePO 4 , Fe 2 O 3 , Li 2 CO 3  (NH 4 ) 2 HPO 4 . etc. Other than elemental carbon, different organic compounds are also used as reducing agents and to increase conductivity (U.S. Pat. No. 7,285,260). 
         [0005]    U.S. Pat. No. 7,338,647 proposes a slurry process method for generating electrode materials. The slurry comprises a polymeric material, a solvent, a polyanion source or alkali metal polyanion source and at least one metal ion source. The slurry is heated for a time sufficient to remove the solvent and form a dried mixture. The mixture is heated to form the electrode material. 
         [0006]    The liquid process category includes a number of different solution processes. Published Chinese patent CN 1773754 discloses a liquid process method. The soluble iron salt, LiH 2 PO 4  and other metal salts are used to make a solution. The solution is spray-dried at a temperature between 300-500° C. In the chamber, LiFePO 4  particles are nucleated and grow up. Published Chinese patent CN 1803590 discloses a method using a solution of soluble metal salts and a phosphorous chelate compound. Published Chinese patent CN 1564347 discloses a liquid-gel processing method. The solution comprises a soluble lithium salt, a source of phosphate and metal nitrates. The organic gel comprises citric acid, polyethylene glycol and glucose. An ultrasonic spray pyrolysis has also been used with nitrate, phosphorous acid and ascorbic acid to make carbon coated LiFePO 4  particles (J. of Power Sources, 159 (2006) 307-311). A co-precipitation method has also been used with nitrates, (NH 4 ) 2 HPO 4 , ascorbic acid and ammonia (J. of Power Sources, 146 (2005) 539-543). Finally, a hydrothermal route has also been used (J. of Power Sources, 165 (2007) 656-659). 
         [0007]    In ceramic processing methods, gel-casting is a well developed method to make ceramic products with a complex shape. This method uses an organic monomer solution to make a slurry with ceramic particles. The slurry is poured into a mold. After the polymerization reaction of the monomer, a gel forms. This 3-dimensional network keeps the ceramic particles in a certain shape for subsequent drying and sintering processes. Polymerization reactions include two major groups: addition (chain-growth) polymerization and condensation (step-growth) polymerization. In condensation polymerization, the chain growth is accompanied by elimination of small molecules such as H 2 O or CH 3 OH. In the addition polymerization process, the polymer is formed without the elimination of side products. Addition polymerization involves the linking together of reactant molecules which incorporate either a double or a triple bond. These unsaturated monomers are able to link up with other monomers or other reactant molecules to form the repeating chain. In addition, there are many variants and subclasses of polymerization reaction. The main forms of addition polymerization are free radical addition and ionic (cationic and anionic) polymerization. The free radicals and ions initiate the polymerization reactions. Free radicals are very reactive atoms or molecules which have an unpaired electron. Free-radical initiation has been most thoroughly studied and is most widely employed. There are many different types or categories of initiators, which produce free radicals to initiate polymerization reactions. Decomposition of hydrogen peroxide is used extensively to generate free radical initiators (“Principals of Polymerization” George Odian, Fourth Edittion). The most simple reaction is the decomposition of H 2 O 2  according to reaction (1) 
         [0000]      H 2 O 2 →2HO.  reaction (1)
 
         [0008]    The activation energy of reaction (1) is high, 220 kJ/mol. Therefore heating is necessary to initiate the reaction. A redox (reduction-oxidation) reaction is extensively used to decrease the activation energy. Metal ions with lower valance are very common reductants. Among them, Fe 2+  ions are often used as in reaction (2). 
         [0000]      H 2 O 2 +Fe 2+ →HO.+OH −1 +Fe 3+   reaction (2)
 
         [0009]    In reaction (2), the oxidation of Fe 2+  produces a hydroxyl and a HO. free radical. The activation energy for reaction (2) is decreased to 40 kJ/mol. Therefore, reaction (2) can be initiated at room temperature without heating. 
       BRIEF OVERVIEW OF THE INVENTION 
       [0010]    In the liquid process, iron nitrate and iron citrate are cheap and soluble iron salts. In the practical process they show some drawbacks. During the decomposition, iron nitrate produces NO and NO 2 , which are strong oxidizers. These oxidizers have a bad effect on the formation of carbon coating on the surface of LiFePO 4  particles. On the other hand, during decomposition in nitrogen atmosphere, citrate produces too much carbon, which results in a poor electrochemical performance. The present invention provides a solid-liquid mixing method to overcome the above drawbacks. 
         [0011]    An organic gel with solid powders has been used as disclosed by Chinese patent CN 1564347. The organic gel method for ceramic synthesis is a well known method, especially for gel-casting, tape casting, slip casting processes. Gel-casting uses a few weight percent of a polymer and makes a high solid volume density (larger than 40%). The gel has higher viscosity than a normal slurry. A ball milling process results in a gel with a very even composition distribution. 
         [0012]    The present invention uses water as solvent and water soluble organics to make organic gel. A solid iron source such as iron oxides and iron hydroxides can be used. Lithium source can be soluble such as LiOH, and can also be insoluble such as Li 2 CO 3 . The phosphorous source can be soluble such as phosphorous acid, phosphor oxide, and different ammonium phosphates. The raw materials and a certain amount of water are loaded into a ball milling jar. The amount of water is enough to dissolve the mixture of lithium compounds, phosphorous compounds and the products by the reaction of these compounds. The main purpose of the milling process is to thoroughly crush agglomerates and form a fully dispersed slurry. The gel forming agents can be added after a defined milling time, which can then be followed by a second milling. The milling process can evenly distribute the raw materials in the gel. The low fluidity of the gel structure prevents the mixture from and/or decreases the composition segregation. Gelation reaction may be initiated just after gelation agents are added into the slurry. It can also be initiated by a post heating process. The gel can then be dried. A spraying dry process can also be used to make dried gel particles. A subsequent calcination process generates the LiFePO 4  particles with a carbon coating or carbon network which can be produced by the decomposition of the organic gel materials. 
     
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         [0013]      FIG. 1  illustrates XRD patterns of the LiFe PO 4 . The patterns are the sample 1, sample 2 and sample 4 by a sequence from bottom to top. 
           [0014]      FIG. 2  illustrates a SEM picture of the sample 1. 
           [0015]      FIG. 3  illustrates a SEM picture of the sample 2. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Technical Description and Supporting Data 
       [0016]    The candidates of metal and phosphor sources include LiOH, Li 2 CO 3 , Fe 2 O 3 , Fe 3 O 4 , Fe(OH) 3 , FeOOH, FeC2O 4 , P 2 O 5 , H 3 PO 4 , NH 4 H 2 PO 4 , (NH 4 ) 2 HPO 4 , etc. Iron compounds are solid particles. Lithium compound and phosphorous compound are pre-dissolved to form a water-solution. Organic gel forming components include monomer, initiator and some additives such as dispersant, catalyst, etc. At first, the solid and solution phases can be milled for several hours. This process can be used to crush all agglomerated solid particles to form a fully dispersed slurry. At the second, gel forming agents are added into the slurry. The polymerization reaction can be immediately initiated or initiated during a subsequent heating process. Then the gel mixture can be dried and calcined to form final product. The slurry with monomer can also be dried by a spraying dry process. During calcinations in a reducing atmosphere, the added organics decompose to form a carbon coating or alternatively network to increase electric conductivity of the LiFePO 4  particles. 
         [0017]    Acrylamide is a popular monomer for gel casting process of ceramics. It is somewhat toxic, and is only used in a basic condition. Acrylic acid monomer is not toxic and can be used in an acidic condition. Therefore, acrylic acid is used as the monomer for gel reaction. Fe 2+  ions may be used as iron source for the products, and used as reductant in the redox reaction (see equation 2). Therefore, hydrogen peroxide, H 2 O 2 , and Fe 2+  compound can be co-added to initiate the gel reaction without heating. 
         [0018]    In the examples, Fe 2 O 3 , Fe 3 O 4 , FeOOH, are used as iron source respectively. FeC2O 4  is used as Fe 2+  additive with Fe 2 O 3 . Li 2 CO 3  and P 2 O 5  are used to make the solution of lithium and phosphorous compounds. The processing procedure is as follows:
       (1) P 2 O 5  is dissolved in water in a glass milling jar.   (2) Li 2 CO 3  is added into the above solution. It will react with P 2 O 5  solution. Then all reaction products must be dissolved in the solution, otherwise, it would segregate with Li and/or P rich components.   (3) Iron compound and milling balls are added into milling jar. Milling process continues overnight.   (4) Acrylic acid and H 2 O 2  are added into slurry. The gelation reaction can start immediately and the polymerization is completed quickly, as indicated by the Fe 2+  ion consumption.   (5) The slurry is milled again for 3 hours. The slurry becomes more viscous after the second milling process.   (6) The slurry, which has not fully polymerized, is heated on hot plate with magnetic stirring. Some more H 2 O 2  droplets are added. The gelation reaction can be gradually initiated at about 70-80° C. The viscosity of slurry can gradually be increased. Finally, the slurry or gel becomes nearly “solidified.”   (7) The gel is dried at 120° C.   (8) The dried mixture can be milled in an agate vial for 30 minutes to obtain a fine powder.   (9) The powders can be calcined at a different temperature in an atmosphere of 5% H 2  with N 2 .   (10) The calcined powders can be milled again in an agate vial to get final particle size.       
 
         [0029]    Sample 1. Reaction of LiFePO 4  from Fe 2 O 3  (50 nm). 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Raw material 
                 Mole ratio 
                 Amount 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Li 2 CO 3   
                 1.03 
                 6.044 
                 g 
               
               
                   
                 Fe 2 O 3   
                 1.00 
                 12.683 
                 g 
               
               
                   
                 P 2 O 5   
                 1.00 
                 11.273 
                 g 
               
               
                   
                 H 2 O 
                   
                 30 
                 ml 
               
               
                   
                 Acrylic acid 
                   
                 4 
                 ml 
               
               
                   
                 H 2 O 2   
                   
                 2 
                 ml 
               
               
                   
                   
               
             
          
         
       
     
         [0030]    After acrylic acid monomer and H 2 O 2  were added into the milled slurry, the slurry became more viscous, but no polymerization occurred. The mixed slurry was heated on a hot plate with stirring. The polymerization reaction occurred at about 70° C. The slurry became more and more viscous. It was finally dried at 120° C. The dried gel was calcined at 650° C. in an atmosphere of 5% H 2  with N 2 . As shown in  FIG. 1 , the XRD of sample 1 reveals a well crystallized olivine type structure. Based on the SEM analysis the particle size is about 100 nm, see  FIG. 2 . 
         [0031]    Sample 2. Reaction of LiFePO 4  from Fe 2 O 3  (50 nm) with FeC 2 O 4  additive. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Raw material 
                 Mole ratio 
                 Amount 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Li 2 CO 3   
                 1.03 
                 6.038 
                 g 
               
               
                   
                 Fe 2 O 3   
                 0.98 
                 12.416 
                 g 
               
               
                   
                 FeC 2 O 4   
                 0.04 
                 0.285 
                 g 
               
               
                   
                 P 2 O 5   
                 1.00 
                 11.261 
                 g 
               
               
                   
                 H 2 O 
                   
                 30 
                 ml 
               
               
                   
                 Acrylic acid 
                   
                 4 
                 ml 
               
               
                   
                 H 2 O 2   
                   
                 1 
                 ml 
               
               
                   
                   
               
             
          
         
       
     
         [0032]    2% FeC 2 O 4  was used to replace Fe 2 O 3 . After acrylic acid monomer and H 2 O 2  were added into the slurry, the polymerization occurred immediately. The milling jar became much warmer. The slurry become very viscous, and lost fluidity. This means FeC 2 O 4  prompted the reaction as shown in equation (2). 
         [0033]    Sample 3. Reaction of LiFePO 4  from Fe 3 O 4  (300 nm). 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Raw material 
                 Mole ratio 
                 Amount 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Li 2 CO 3   
                 1.03 
                 4.089 
                 g 
               
               
                   
                 Fe 3 O 4   
                 1.00 
                 8.285 
                 g 
               
               
                   
                 P 2 O 5   
                 1.00 
                 7.626 
                 g 
               
               
                   
                 H 2 O 
                   
                 30 
                 ml 
               
               
                   
                 Acrylic acid 
                   
                 3 
                 ml 
               
               
                   
                 H 2 O 2   
                   
                 1 
                 ml 
               
               
                   
                   
               
             
          
         
       
     
         [0034]    After acrylic acid monomer and H 2 O 2  were added into the milling jar, the reaction immediately occurred as in the example 2. This means Fe 2+  ions in Fe 3 O 4  partially dissolved and prompted the reaction as shown in equation (2). As shown in  FIG. 1 , the XRD of sample 2 reveals a well crystallized olivine type structure. Based on the SEM analysis the particle size is about 100 nm, see  FIG. 3 . 
         [0035]    Sample 4. Reaction of LiFePO 4  from FeOOH (amorphous). 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
               
             
           
               
                   
                   
               
               
                   
                 Raw material 
                 Mole ratio 
                 Amount 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Li 2 CO 3   
                 1.03 
                 5.769 
                 g 
               
               
                   
                 FeOOH 
                 1.00 
                 13.471 
                 g 
               
               
                   
                 P 2 O 5   
                 1.00 
                 10.760 
                 g 
               
               
                   
                 H 2 O 
                   
                 40 
                 ml 
               
               
                   
                 Acrylic acid 
                   
                 10 
                 ml 
               
               
                   
                 H 2 O 2   
                   
                 2 
                 ml 
               
               
                   
                   
               
             
          
         
       
     
         [0036]    FeOOH releases H 2 O when it decomposes. H 2 O will oxidize the carbon produced from the decomposition of acrylic acid. Therefore, more acrylic acid was used than with the other iron sources. As shown in  FIG. 1 , the XRD of product reveals a well crystallized olivine type structure.