- LiFe y Ti x Mn 2-x-y O 4 (0x, y1)

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! 3 3 / ' '/' «1» '' %* 1 4 / 1 4 3 " 1 ' LiMn 2 O 4 3 1 ~ 4! Li)! 4 4 ' * 1 3 1 3d LiFe y Mn 2y O 4 0 < y 05) 3 ' 3 47 51! Li [1] ' Fe 3+ /Fe 4+ : '' 1 LiFe y Mn 2y O 4 ' 4! ' Mn 3+ /Mn 4+ ) * ' ~5! + 4 1 1 LiFeMnO 4 1 LiMn 2 O 4 ) 1 47 5!! 4 5 1 3 ) * LiFeTiO 4 [2] LiMnTiO 4 [3] C Li 4 Ti 5 O 12 3 4 ' ~ 17 2! Li [4]" LiFeMnTi) 2 O 4 Fd3m) 1 * 3 * 4 ' 6/ LiFe Ti Mn) 2 O 4 1

4 " 3* 73 * LiFe y Ti x Mn 2xy O 4 0 y 1) ) ' 4 #5 LiFe y Ti x Mn 2xy O 4 0 y 1)!) 3 3*:! LiFe Mn Ti) 2 O 4 * * 4 1 ' 4 4 1 4 + 1 ' '' 1 4 ' 4 4 ' 4 : 3* 1 * ' ; 3 ' 4 4 6 4 1 4 8 / ) ' /' + ) # $ ) 1

$ 03211845) $ ' 9 8320) INTAS 9 YF 05 1095341) $& 02513113246) # $ 2006 * 3* 1: & 1 ' LiFe Mn Ti) 2 O 4! 4 LiFe y Ti x Mn 2xy O 4 0 y 1) 4 4 ' 3 4 4 ' 4 ' $ 1 ' 1 ):"" # $ 1 1 : International Symposium on New Trends in Intercalation Compounds for Energy Storage and Conversion 205 th the Electrochemical Society Meeting 30 April 2 May 2003 Paris France; III IV # $ +# $ 2003; % 2004) II International Conference "Mechanochemical Synthesis and Sintering" 1517 June 2004 Novosibirsk; 7 8 1 * «&» 1618 3 2004 1316 3 2006 8 ; International Conference on Solid State Chemistry 1415 Sept 2004 Prague Czech Rep;! c ' ": ' 2004" %; VIII 1 ' «& 4 4» 57 2004 ;! ' ' ") " 1617 2005 ; 15 th International Conference on Solid State Ionics SSI15) 1722 July 2005 BadenBaden Germany; V International Conference on Mechanochemistry and Mechanical Alloying INCOME2006) July 36 Novosibirsk; Topical Meeting of the European Ceramic Society Structural Chemistry of Partially Ordered Systems Nanoparticles and Nanocomposites June 2729 2006 St Petersburg; 8 th International Symposium on Systems with Fast Ionic Transport 8 th ISSFIT) 2327 May 2007 Vilnius Lithuania; 16 th International Conference on Solid State Ionic SSI16) 16 July 2007 Shanhai China! ' 1 20022007

'! 1 ):"" # $ : " 3 ;;; +; )0 # $! 7; 60 + / ); 3 + ) ' ' 29 4 ' 6 19 1 ' 5 /' 5 1 ' ' ' 1 ' 1 * * 3* 4 4 4 LiMn 2 O 4 4 # 1 ' 4 # 3* LiFe Mn Ti) 2 O 4 3 3* ) ' / 5 ' ' " LiFe y Ti x Mn 2xy O 4 0 x y 1) : «auto ignition» ): ' LiOH H 2 O MnO 2 TiO 2 ) Fe 2 O 3 xh 2 O/γFe 2 O 3 ' A#2 5 650 o C 10

1 1 750 o C 15 ): 3! [5] 3 4 ' 1 ')! 3 3* : LiNO 3 FeNO 3 ) 3 9H 2 O TiO 2 ) MnNO 3 ) 2 H 2 O/ MnC 2 H 3 O 2 ) 2 4H 2 O) ) 3 25 0 / 700 0 1 4 20 ' ' :! P123 µ =5800 / )! FeSO 4 7H 2 O/FeCl 2 4H 2 O LiOH H 2 O MnNO 3 ) 2 H 2 O TiC 12 H 28 O 4 ) 3* : 1 < ) P123 0013 4 ) ' 4 C 2 H 6 O 2 12 4 1 < ) * 24 ) # 9 700 ' 3* : ) /$#4 Co Cu Kα Bruker D8 ADVANCE Cu Kα 5 2Θ=1575 0 ' Li Fe Mn Ti) Varian 280 FS 1 Mn 3+ *3 4 Philips CM30T JEM 2000FX LaB 6 1 200300! 1 )!" NZ640/2!$) 1 300 0) α Fe ) 57 Co ' Cr ' 1 1 *

# ' 4 4 10 2 ' Hewlett Packard 4284A Precision LCRMeter 300 550 0 " : 3 ± 05 0 #$ CR2320 Hohsen) 1 4 LiPF 6 1M) EC/DMC 1:2) 001 03 /c 2 0 3 '3 Solvay) Carbon black >999% <10 =m; Alfa) 01 mm; Fluka) 80:10:3:7; 3* ' 12 NMP MerckSchuchardt) 3 * 15 33 * 200 µ 80 0 3 * 70 = 4 14 #$ $ > ' 4 05LiClO 4 05Al 2 O 3 [6] «4» 400 3* 200 0 1 / 4 4 ' * Al Ni V '' 1040 5 % / 4 4 4 1 4 1020 5 %! / 05LiClO 4 05Al 2 O 3 / 0 5! 200 *3 $ 2 1 0 5! 3 210!/ 3 APPA 107!%& $ ; 40 *3 ' 1 : Li Mn Fe Ti! LiFe 3+ ymn 4+ 1δMn 3+ 1+δyO 405δ 0 < y < 1)

$ 1 LiFe y Ti x Mn 2xy O 4 0 x y 1) δ δ max =02) : LiFe y Ti x Mn 2xy O 4 0 x y 1) 0 3* LiOH?H 2 O: Li 7% Fe8% Mn27% Ti13% *3 1) * $ 2 # * 3 * LiFeTiO 4 LiFeMnO 4 LiMn 2 O 4 * LiFeTiMn) 2 O 4 2)! ' 1

Fd3m) 4 a c '' 1 3 09 < y < 11; x = 0 3) a c 1 1* ' x = 0; 0 y 05) 3 [1]; LiFeTiO 4 a c = 8362±0002Å) [2] ' LiFeMnO 4 3 1 Li 2 MnO 3 ' 1 4 ' 2[Mn Mn4+ ] x x + O O 2[Mn 3+ Mn ]' + V O + 1 / 2 O 2 '' Mn 3+ $ 3 LiFe y Ti x Mn 2xy O 4 0 x y 1) '' ' $ 4 LiFe y Ti x Mn 2xy O 4 x=0)! '' 1 $ LiFe y Ti x Mn 2xyO 4 0 < x y < 1) 4 ; LiFe y Ti x Mn 2xy O 4 *3 4 3 01 < y < 06 x=0) y > 06 3 : MnNO 3 ) 2 H 2 O Li 2 MnO 3 ' ' 3

6 4 5 '! ' / ' Mn2+ Mn4+)! ' 3* 1 1 : y > 06) 3 ' ac 3 4) LiMn2O4 ' * 3 4 ) *» ' LiFeyTixMn2yxO4 0 < x y < 1) * 3 4 5 $ ' LiFe05Mn15O4 3* ' LiFe07Mn13O4 LiTiMnO4 ' 100200 2 3) "! 100 ' «1); 1 $ 5 6!: LiFe07Mn13O4 2) 2 ' LiFe05Mn15O4 1); LiTiMnO4 3) ' ' ' % % $ 4 LiFeyTixMn2yxO4 0 < y 1 x=0) 3 3 3* 50 3 " 1 1 *! " $ 6) : '

1 1 0 07 1 4 16d '! 07 < y 1 $ 6 4 ' y07 y>07 a ) * [Fe 3+ tetra]) '' ' ': 3 4 1! LiFe y Ti x Mn 2yx O 4 01 y 05 x=0) 3 3 1 " LiFe y Ti x Mn 2yxO 4 01 y 1) 78) # 4 ' 4 ' '' 4 '' ' 21227 0 6 ' '' ' 0916 4! LiFeTiO 4 ) 0294! LiMn 2 O 4 ) 1 5 ' Mn 3+ ' Mn 4+ ) Mn 3+ 3 ' 3* 4 1 1 5 43 '

$ 7 LiFe y Ti x Mn 2xy O 4 0 x y 1) $ 8 LiFe y Ti x Mn 2yx O 4 0 x y 1) '' ' 203 0!!%& "$$ $ % " ' % " 6 LiFe y Ti x Mn 2yx O 4 0 x y 1) 0! 1 4 7 4 Li/LiFe y Ti x Mn 2xy O 4 0 x y 1) 4 4 : 35 495!! 4 1 4 4 13 ' '/' ) 9 3* 4 ': / 1 1* 9 ; %)): ' / ' Mn 3+ /Mn 4+ : LiFe y Ti x Mn 2xy O 4 <=>Li y [Fe y Ti x Mn 2yx ]O 4 + 1y)Li + +1y)e 42! 1) 3* Fe 3+ /Fe 4+ '

Li y [Fe y Ti x Mn 2yx ]O 4 <=>[Fe y Ti x Mn 2yx ]O 4 + yli + + ye 47 5! 2); / LiTiMnO 4 9! )): LiTi x Mn 2x O 4 <=>V Li [Ti x Mn 1x O] 4 + Li + +e 4042! 3); / LiFeTiO 4 9/)): LiFeTiO 4 + Li + + e <=> Li 2 FeTiO 4 1625! 4) 4042! 1 '' ' III) 4750!) '' 1 " $ 9 LiFe 05 Mn 15 O 4 ;) LiTiMnO 4! ) LiFeTiO 4 /) LiFe 04 Ti 01 Mn 15 O 4 %) 0 ')! ') 1 1* ' 0

! 3 3 ' 3 3 6 53 ' *3 : ' ' ' 4 ' 1 ' 9 %) 1 1* # ' 3 4 ' ' 6 4 5 3* Mn 4+ ' ) Fe 4+ ' 4 ) #$ " " 4 3 # 3 3;! 4 4 ' 3 ' 4 05LiClO 4 05Al 2 O 3 3 150220 0 Li 5 Ti 4 O 12 / 05LiClO 4 05Al 2 O 3 / LiMn 2 O 4 1) LiMn 2 O 4 / 05LiClO 4 05Al 2 O 3 /LiFe 08 Mn 12 O 4 2) LiMn 2 O 4 / 05LiClO 4 05Al 2 O 3 / LiMn 2 O 4 3) 190 0 10! Li 5 Ti 4 O 12 6/ 22! 6/ Li/Li + /LiMn 2 O 4 4!) Li/Li + /Li 5 Ti 4 O 12 17!) 10 LiFe 08 Mn 12 O 4 1) 2) ' 4 LiFe 08 Mn 12 O 4 ' 4 ' 6 1 5 '' Mn 4+ 3* ' 1)) 3* ; 3* 4 : )LiMn 2 O 4 / 05LiClO 4 05Al 2 O 3 / LiMn 2 O 4 +) )

)Li 4 Ti 5 O 12 / 05LiClO 4 05Al 2 O 3 / LiFe 05 Mn 15 O 4 +) ;); $ 11! 4 3 3* ': : LiMn 2 O 4 + xli + + e <=> Li 1+x Mn 2 O 4 ~ 3! Li/Li + ); Li 4 Ti 5 O 12 + 3e +3Li + <=> Li 7 Ti 5 O 12 ; ~ 17! Li/Li + ); : LiMn 2 O 4 <=> xli + + Li 1x Mn 2 O 4 + xe ~ 3942! Li/Li + ); LiFe 05 Mn 15 O 4 <=> xli + + Li 1x Fe 05 Mn 15 O 4 + xe ; 4 ~ 5! Li/Li + ) $ 10 ) 13; ) ' LiFe 08 Mn 12 O 4 1) 2) ' 4 1 002 005 001 / 2 ; 4 7 $ 11! )" ;) ' 10!/ ' 10!/) 3 ~16! 3* ' ' LiMn 2 O 4 11 )) ' 6/ 15! % LiFe 05 Mn 15 O 4 2

3* 4 ' Mn 3+ /Mn 4+ Fe 3+ /Fe 4+ ' 6/ ; ~29! 11 ;)) ' 4 ' 1 4 4 ' #$%& 1! LiFe y Ti x Mn 2xy O 4 0 y1)!)! 4 2 # * * * LiMnFeTi) 2 O 4 + 3 4 ' 1 1 y 07) LiFe y Ti x Mn 2xy O 4 Fe 3+ 3 4 16d ' / '' 1 3 4 Fe 3+ 3 4 #1 ' 1 '' ' LiFe y Ti x Mn 2xyO 4 0 y1); 4 '' ' * 5! LiFe y Ti x Mn 2xy O 4 0 y 1) 4 * 0 3 / 3 ' 3 3 ' 40200 ) 6 #* 4 ' 4 4 ' 4

')! 1 T Ohzuku K Ariyoshi S Takeda YSakai // Electrochimica Acta 2001 V 46 P 23272336 2 Crystal structure and electrical properties of LiFeTiO 4 / MA Arillo ML Lopez E PerezCappe C Pico ML Veiga // Solid State Ionics 1997 V 107 P 307312 3 Structural characterisation and physical properties of LiMMnO 4 M=Cr Ti) spinels / MA Arillo G Guello ML López P Martin C Pico ML Veiga // Solid State Sciences 2005 V 7 Issue 1 P 2532 4 Li Insertion into Li 4 Ti 5 O 12 SpinelCharge Capability vs Particle Size in ThinFilm Electrodes / L Kavan J Prochazk TM Spitler MKalba M Zukalova T Drezen M Gratzel // J of The Electrochem Soc 2003 V150 7) P A1000A1007 5 1 ' 8 : ) 1998 512 6 Composite solid electrolytes LiClO 4 Al 2 O 3 / AS Ulihin NF Uvarov Yu G Mateyshina LI Brezhneva AA Matvienko // Solid State Ionics 2006 V177 P 2787 2790 # ' 3 * : 1 1 1* ' / &+ "3 // : 2005 2 C 295298 2 Electrochemical modification of spinel oxide materials using lithium solid state electrolyte/ Yu G Mateyshina NF Uvarov AS Ulihin Yu T Pavlyukhin // Solid State Ionics 2006 V177 P 2769 2773 3 Composite solid electrolytes LiClO 4 Al 2 O 3 / AS Ulihin NF Uvarov Yu G Mateyshina LI Brezhneva AA Matvienko // Solid State Ionics 2006 V177 P 2787 2790 4 Solid state electrochemical lithium cells with oxides electrodes and solid composition electrolyte/ Yu G Mateyshina NF Uvarov AS Ulihin // 6 2007 V43 95 P634637 5 Synthesis and characterization of new ironcontaining materials for 5V lithium batteries/ Yu G Mateyshina N F Uvarov// In: New trends in intercalation compounds for energy storage conversion ed by K Zaghib C M Julien J Prakash) Proc Intern Symp Paris France 30 April 2 May 2003) Electrochem Soc Pennington V 200320 P529533 6 6 ' / &+ "3 //& 4 4 VI 1 ' 56 2005) 2005 234236 7 " 4 4 LiClO 4 Al 2 O 3 / + 81 &+ // & 4 4

VI 1 ' 56 2005) 2005 237239 8 4 / + //! ' ' «)» 1617 2005) 2005 207211 9 ' / & + // " 1 1 6 1 ' 1215 2005) C 98101 10 " 4 4 LiClO 4 Al 2 O 3 / + // " 1 1 6 1 ' 1215 2005) C 102104 11 Synthesis and characterization of new ironcontaining materials for 5V lithium batteries / Yu G Mateyshina N F Uvarov // International Symposium on New trends in intercalation compounds for energy storage conversion Paris France 30 April 2 May 2003) Paris 2003 12 Mechanochemical synthesis of ironcontaining lithium spinels/ YuGMateyshina NFUvarov YuTPavlyukhin// II Intern Conf on Fundamental Bases of Mechanochemical Technologies "Mechanochemical synthesis and sintering" Novosibirsk Russia 1517 June 2004) Novosibirsk 2004 P185 13 Transport properties of solid solutions LiFe x Mn 2x O 4 / YuGMateyshina NFUvarov YuTPavlyukhin // 7th Meeting «Fundamental Problems of Solid State Ionics" Chernogolovka Russia 1618 June 2004) Chernogolovka 2004 14 Structure and electrochemical properties of solid solutions LiFe 1y Ti 1 xmn x+y O 4 / YuGMateyshina NFUvarov YuTPavlyukhin // Conf on Solid State Chemistry Prague Czech Rep 1415 Sept 2004) Prague 2004 15 Crystal Structure and Transport Properties of Solid Solutions LiFe X Mn 2 XO 4 / YuGMateyshina NFUvarov YuTPavlyukhin // 4th Intern Conf on Inorganic Materials Antwerpen Belgium 1921 Sept 2004) Antwerpen 2004 16 ) LiFe 1y Ti 1x Mn x+y O 4 / + & 3 "// Vlll 1 ' «& 4 4» % 57 2004) % 2004 17 6 ' / &+ "3 // VI 1 0 «& 4 4» 59 2005 ) 2005 234236 18 4 / + //! ' ' «)» 1617 2005) 2005 207211 19 ' / + & // " 1 1 6 1 ' 1215 2005 C 98101

20 " 4 4 LiClO 4 Al 2 O 3 / + // 1 102104 21 6 ' 4 4 LiClO 4 Al 2 O 3 / &+ "3 81 // IV C C# $ +# $ "" " 26 28 c 2005 ) 2005 22 Composite solid electrolytes LiClO 4 Al 2 O 3 / ASUlihin NFUvarov YuGMateyshina LIBrezhneva AAMatvienko // XV Intern Conference on Solid State Ionics SSI15) BadenBaden Germany 1722 July 2005) BadenBaden 2005 P435 23 Effect of mechanical activation on cation distribution in lithium ironmanganese spinels / YuG Mateyshina YuT Pavlyukhin N F Uvarov // V International Conference on Mechanochemistry and Mechanical Alloying INCOME 2006) Novosibirsk Russia July 36 2006) Novosibirsk 2006 P 124 24 Solid state electrochemical lithium cells with oxide electrodes and composite solid electrolyte/ YuG Mateyshina NF Uvarov AS Ulihin // Abstracts of 8 th International Meeting Fundamental Problems of Solid State Ionics Chernogolovka Russia June 1316 2006) Chernogolovka 2006 P301302 25 Nanocomposite solid electrolytes for intermediate temperature lithium batteries / YuGMateyshina ASUlihin NYuShestakova NFUvarov // Abstracts of Topical Meeting of the European Ceramic Society Structural Chemistry of Partially Ordered Systems Nanoparticles and Nanocomposites St Petersburg Russia June 2729 2006) St Petersburg 2006 P136 26 Influence of the chemical nature of nanocrystalline oxide on ionic conductivity of composite solid electrolytes based on LiClO 4 / AS Ulihin YuGMateyshina LI Brezhneva NFUvarov OAKharlamov VPIsupov // Abstracts of 2 Russian Conference on Nanomaterials NANO2007)Novosibirsk Russia 1316 March 2007) Novosibirsk 2007 P 401 27 Autoignition synthesis and investigation of nanocrystalline complex lithium oxides / YuGMateyshina NFUvarov BBBokhonov YuTPavlyukhin ULafont EM Kelder // Abstracts of 2nd Russian Conference on Nanomaterials NANO2007) Novosibirsk Russia 1316 March 2007) Novosibirsk 2007 P 191 28 Physical and electrochemical properties of lithium manganeseiron oxides prepared by different methods / YuGMateyshina ULafont NF Uvarov E M Kelder // Abstract of 8 th International Symposium on Systems with Fast Ionic Transport 8 th ISSFIT) Vilnius Lithuania 2327 May 2007) Vilnius 2007 P 89 29 Crystal structure and electrochemical properties of solid solutions in the system LiMn 2 O 4 LiFe 2 O 4 LiTi 2 O 4 / YuGMateyshina NFUvarov BBBokhonov ULafont EM Kelder // Abstract 16 th International Conference on Solid State Ionic SSI16) Shanhai China 16 July 2007) Shanhai 2007 P754

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