United States Patent (19)
`Idota et al.
`
`III III-III
`US005618640A
`11
`Patent Number:
`5,618,640
`(45) Date of Patent:
`Apr. 8, 1997
`
`(54) NONAQUEOUS SECONDARY BATTERY
`(75) Inventors: Yoshio Idota; Masayuki Mishima;
`Yukio Miyaki; Tadahiko Kubota;
`Tsutomu Miyasaka, all of Kanagawa,
`Japan
`(73) Assignee: Fuji Photo Film Co., Ltd., Kanagawa,
`Japan
`
`21 Appl. No.: 326,365
`(22) Filed:
`Oct. 20, 1994
`(30)
`Foreign Application Priority Data
`Oct. 22, 1993
`(JP)
`Japan .................................... 5-264995
`Jan. 27, 1994 (JP
`Japan .................................... 6-007760
`Feb. 24, 1994 (JP
`Japan .................................... 6-026745
`Feb. 28, 1994
`JP
`Japan .................................... 6-030206
`Mar. 11, 1994 (JP)
`Japan .................................... 6-066422
`(5ll Int. Cl. .......................................... HO1M 6/14
`52 U.S. Cl. ................................ 429/194; 429/218; 419/1
`(58) Field of Search ..................................... 429/218, 194,
`429/217; 252/182.1; 41.9/1, 26, 54
`
`56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`1/1979 Eisenberg ............................ 429/218 X
`4,136,233
`4,142,028 2/1979 Leger et al. ...
`... 429,194
`4,495,258
`1/1985 Michaute et al. ...
`429/194X
`4,751,158 6/1988 Uchiyama et al. .
`429/218 X
`4,808,498 2/1989 Tarey et al. .....
`... 429/218
`4,808,499 2/1989 Nagai et al. ...
`... 429/218
`5,057,387 10/1991 Masuda et al. .
`429/218 X
`5,196,278 3/1993 Idota ....................................... 429/194
`
`5,283,136 2/1994 Peled et al. ......................... 429/218 X
`5,284,721
`2/1994 Beard ...................................... 429/194
`5,300,376 4/1994 Plichta et al. ....................... 429/194X
`FOREIGN PATENT DOCUMENTS
`05821.73 2/1994 European Pat. Off..
`0615296 9/1994 European Pat. Off. .
`OTHER PUBLICATIONS
`Proceedings of the Symposium on High Power, Ambient
`Temperature Lithium Batteries, Phoenix, Arizona, Oct.
`13-17, 1991, vol. 92-15, pp. 101-112.
`Primary Examiner-Anthony Skapars
`Attorney, Agent, or Firm-Sughrue, Mion, Zinn, Macpeak &
`Seas
`ABSTRACT
`(57
`A nonaqueous secondary battery comprising a positive elec
`trode active material, a negative electrode active material,
`and a lithium salt is disclosed, in which the negative
`electrode active material contains (1) a compound capable of
`intercalating and deintercalating lithium comprising an atom
`of the group IIIB, IVB or VB of the periodic table, (2) an
`amorphous compound containing at least two atoms selected
`from the elements of the groups IIIB, IVB, and VB of the
`periodic table, (3) a compound capable of intercalating and
`deintercalating lithium containing at least one of the atoms
`of the group IIIB, IVB, and VB of the periodic table and
`fluorine, or (4) a compound of the metal of the group IIIB,
`IVB or VB of the periodic table, Zn, or Mg which is capable
`of intercalating and deintercalating lithium. The nonaqueous
`secondary battery of the invention exhibits improved charge
`and discharge characteristics and improved safety.
`
`9 Claims, 2 Drawing Sheets
`
`2
`
`
`
`24444444
`
`2
`
`Ky 32
`elessessess2
`4222222222222222222222
`
`Samsung Ex. 1023, Page 1 of 26
`Samsung Electronics Co., Ltd. v. RJ Technology, LLC
`IPR2023-01183
`
`

`

`U.S. Patent
`
`Apr. 8, 1997
`
`Sheet 1 of 2
`
`5,618,640
`
`OOOZ).
`OO’O9
`
`OO OG
`
`|
`
`O O’Otz
`
`———
`
`----+
`
`|
`
`
`
`
`
`XAOO’G
`
`ScHO
`
`Samsung Ex. 1023, Page 2 of 26
`Samsung Electronics Co., Ltd. v. RJ Technology, LLC
`IPR2023-01183
`
`

`

`U.S. Patent
`
`Apr. 8, 1997
`
`Sheet 2 of 2
`
`5,618,640
`
`F. G. 3
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`''. SysAga Sassy
`), ZAZZZZZZZZ
`''. ZCZZzzzzzzz
`S447 &
`
`g-ter
`273) :
`
`Sakk .:
`ZZZZZZZA2 - ,
`
`3.
`
`
`
`
`
`
`
`
`esseeseese s2
`g22 et elee-ee-eate-ee-ee-eate
`
`.
`
`.
`
`.
`
`. .
`
`.
`
`.
`
`.
`
`.
`
`.
`
`.
`
`.
`
`
`
`.
`
`. . ."
`
`.
`
`.
`
`.
`
`s.
`
`Samsung Ex. 1023, Page 3 of 26
`Samsung Electronics Co., Ltd. v. RJ Technology, LLC
`IPR2023-01183
`
`

`

`1.
`NONAQUEOUS SECONDARY BATTERY
`
`FIELD OF THE INVENTION
`This invention relates to a nonaqueous secondary battery
`having improved charge and discharge cycle characteristics
`and improved safety.
`
`O
`
`15
`
`20
`
`25
`
`BACKGROUND OF THE INVENTION
`Negative electrode active materials for nonaqueous sec
`ondary batteries typically include metallic lithium and
`lithium alloys. The problem associated with these active
`materials is that metallic lithium grows dendritically during
`charging and discharging to cause an internal short circuit,
`involving a danger of ignition because of high activity of the
`dendritical metal per se. To solve the problem, a calcined
`carbonaceous material capable of intercalating and deinter
`calating lithium has recently been put to practical use.
`However, since the carbonaceous material has electrical
`conductivity by itself, metallic lithium is sometimes pre
`cipitated on the carbonaceous material at the time of an
`overcharge or a rapid charge. It eventually follows that
`lithium grows dendritically thereon. This problem has been
`dealt with by altering a charger or reducing the amount of the
`positive electrode active material to prevent an overcharge.
`Where the latter solution is adopted, however, the limited
`amount of the active material leads to a limited discharge
`capacity. Further, the carbonaceous material has a relatively
`low density and therefore a low capacity per unit volume.
`Thus, the discharge capacity is limited by both the amount
`of the active material and the capacity per unit volume.
`In addition to metallic lithium, lithium alloys and the
`above-mentioned carbonaceous material, negative electrode
`active materials so far proposed include TiS and LiTiS,
`which are capable of intercalating and deintercalating
`lithium (U.S. Pat. No. 3,983,476); transition metal oxides
`having a rutile structure, such as WO (U.S. Pat. No.
`4,198,476), spinel compounds, such as LiFe(Fe)O (JP
`A-58-220362, the term "JP-A' as used herein means an
`"unexamined published Japanese patent application'); a
`electrochemically synthesized lithium compound of Fe2O
`(U.S. Pat. No. 4,464,447); a lithium compound of Fe2O
`(JP-A-3-112070); NbO (JP-B-62-594.12 (the term “JP-B”
`as used herein means an "examined published Japanese
`patent application') and JP-A-2-82447); FeO, Fe2O3,
`FeO, CoO, CoO, and CoO (JP-A-3-291862); amor
`phous VO (JP-A-4-223061); and transition metal oxides
`having their basic crystal structure changed by intercalation
`of a lithium ion (EP 567149). Any of these known com
`50
`pounds has a high oxidation-reduction potential, failing to
`provide a nonaqueous secondary battery having a discharge
`potential as high as 3 V and a high capacity.
`SnO or Sn compounds are used as an active material of
`lithium batteries as in LioCoogsSnooO2 as a secondary
`battery positive electrode active material (EP 86-106301);
`SnO-added VO as a secondary battery positive electrode
`active material (JP-A-2-158056); SnO-added o-FeO
`(preferred SnO content: 0.5 to 10 mol %) as a secondary
`battery negative electrode active material (JP-A-62
`-219465); and SnO as a primary battery positive electrode
`active material (Denki Kagaku oyobi Kogyo Butsuri
`Kagaku, Vol. 46, No. 7, p. 407 (1978)). With reference to the
`use of SnO, or Sn compounds as an electrochromic elec
`trode, it is known that SnO is capable of reversible inter
`calation of an Li ion (see Journal of Electrochemical Soci
`ety, Vol. 140, No. 5, L81 (1993) and that a film comprising
`
`35
`
`40
`
`45
`
`55
`
`60
`
`65
`
`5,618,640
`
`2
`InO doped with 8 mol % of Sn (i.e., ITO) is capable of
`reversible intercalation of an Li ion (see Solid State Ionic.,
`Vols. 28–30, p. 1733 (1988)). However, the electrode useful
`in an electrochromic system should be transparent, the
`active material is used in the form of a thin film formed by,
`for example, vacuum evaporation, and the electrode usually
`works at a considerably low current differing from the
`practical range of batteries. For example, Solid State Ionics,
`supra, shows a working current of 1 uA to 30 A/cm’ as an
`experimental example.
`Known positive electrode active materials include spinel
`compounds disclosed in JP-B-4-301.46 and cobalt oxide
`disclosed in JP-B-63-59507.
`It is possible to combine these positive electrode active
`materials with an oxide mainly comprising Sn as a negative
`electrode active material to provide a nonaqueous secondary
`battery having a high discharge potential, a high capacity,
`improved charge and discharge cycle characteristics, and
`increased safety. Yet, the charge and discharge cycle char
`acteristics are still unsatisfactory as described above, and it
`has been keenly demanded to further improve charge and
`discharge cycle characteristics.
`
`SUMMARY OF THE INVENTION
`An object of the present invention is to provide a non
`aqueous secondary battery having improved charge and
`discharge cycle characteristics, a high discharge potential, a
`high discharge capacity, and increased safety.
`The above object of the present invention is accomplished
`by a nonaqueous secondary battery comprising a positive
`electrode active material, a negative electrode active mate
`rial, and a lithium salt, in which (1) the negative electrode
`active material contains at least one compound capable of
`intercalating and deintercalating lithium mainly comprising
`an atom of the group 13, 14, or 15 (as referenced by the
`American Chemical Society format) of the periodic table,
`(2) the negative electrode active material mainly comprises
`an amorphous compound containing at least two atoms
`selected from the elements of the groups 13, 14, and 15 of
`the periodic table, (3) the negative electrode active material
`is a compound capable of intercalating and deintercalating
`lithium containing at least one of the atoms of the group 13,
`14, and 15 of the periodic table and fluorine, or (4) the
`negative electrode active material contains at least one
`compound of the atom of the group 13, 14, or 15 of the
`periodic table, Zn, or Mg which is capable of intercalating
`and deintercalating lithium.
`
`BRIEF DESCRIPTION OF THE DRAWING
`FIG. 1 is the X-ray diffraction pattern of compound D-1-A
`prepared in Synthesis Example D-1.
`FIG. 2 is a cross section of a coin battery prepared in
`Examples, wherein 1 indicates a negative electrode sealing
`plate, 2 indicates a negative electrode active material mix
`ture pellet, 3 indicates a separator, 4 indicates a positive
`electrode active material mixture pellet, 5 indicates a col
`lector, 6 indicates a positive electrode case, and 7 indicates
`a gasket.
`FIG. 3 is a cross section of a cylindrical battery prepared
`in Examples, wherein 8 indicates a positive electrode sheet,
`9 indicates a negative electrode sheet, 10 indicates a sepa
`rator, 11 indicates a battery case, 12 indicates a battery cover,
`13 indicates a gasket, and 14 indicates a safety valve.
`
`Samsung Ex. 1023, Page 4 of 26
`Samsung Electronics Co., Ltd. v. RJ Technology, LLC
`IPR2023-01183
`
`

`

`3
`DETAILED EDESCRIPTION OF THE
`INVENTION
`The terminology "negative electrode active material pre
`cursor as used herein is explained below. The inventors
`have found that SnO having an o-PbO structure, SnO,
`having a rutile structure, and the like do not act by them
`Selves as a negative electrode active material of a secondary
`battery but change their crystal structure on intercalation of
`lithium to act as a reversible negative electrode active
`material. That is, the charge and discharge efficiency of the
`first cycle is as low as about 80% or 60%. Thus, the starting
`material, such as O-PbO-structure SnO or rutile-structure
`SnO, namely, a compound before lithium intercalation is
`called a "negative electrode active material precursor'.
`The negative electrode active material according to the
`present invention can be obtained by electrochemically
`intercalating a lithium ion into, for example, an oxide, an
`active material precursor. Lithium ion intercalation is con
`ducted until the basic structure of the oxide is changed (for
`example, until the X-ray diffraction pattern changes) and
`also until the thus changed basic structure of the Li ion
`containing oxide undergoes substantially no change during
`charging and discharging (for example, the X-ray diffraction
`pattern does not change substantially). The change in basic
`Structure means change from a certain crystal structure to a
`different crystal structure or from a crystal structure to an
`amorphous structure.
`Where the compound represented by formulae (I) to (V)
`of the present invention described in later is used as a
`negative electrode active material precursor, it was found
`that intercalation of lithium does not cause reduction of the
`respective metal (an alloy with lithium). This can be con
`firmed from the fact that (1) observation under a transmis
`sion electron microscope reveals no precipitation of a metal
`(especially no precipitation of a dendrite), (2) the potential
`of lithium intercalation/deintercalation via a metal is differ
`ent from that of the oxide, and (3) the lithium deintercalation
`loss with respect to lithium intercalation in SnO was about
`1 equivalent, which does not agree with a loss of 2 equiva
`lents in the case where metallic tin is generated. Since the
`potential of an oxide is similar to that of a currently
`employed calcined carbonaceous compound, it is assumed
`that the bonding state of lithium is neither mere ionic
`bonding nor mere metallic bonding, similarly to a calcined
`carbonaceous compound. Accordingly, the negative elec
`trode active material of the present invention is obviously
`different from conventional lithium alloys.
`It is preferable that the active material precursor which
`can be used in the present invention is substantially amor
`phous at the time of battery assembly (before lithium ion
`intercalation). The term "substantially amorphous' as used
`herein means that an X-ray diffraction pattern using CuKo.
`rays shows a broad scattering band with peaks between 20
`and 40 in terms of 26 and may contain diffraction assigned
`to a crystalline structure.
`The maximum intensity of the peaks assigned to the
`crystalline structure appearing between 20=40° and 70° is
`preferably not higher than 500 times, still preferably not
`higher than 100 times, still more preferably not higher than
`5 times, the intensity of the peak of the broad scattering band
`appearing between 20=20° and 40°. It is the most preferred
`that the pattern exhibits no crystalline diffraction spectrum.
`Also, it is preferred that the active material precursor is
`Substantially amorphous at the time of intercalating lithium
`ion.
`In the present invention, either the active material pre
`Cursor or the active material can be used as a negative
`
`4
`electrode. Hereinafter, cases are met in which they are
`represented as an active material.
`The metals of the groups 13 to 15 of the periodic table
`which can be used in the present invention include B, Al, Ga.,
`In, Tl, Si, Ge, Sn, Pb, PAs, Sb, and Bi, preferably B, Al, Si,
`Ge, Sn, Pb, P. As, Sb, and Bi, still preferably Al, Si, Ge, Sn,
`Pb, AS, and Sb or B, Al, Si, Ge, Sn, and P.
`Examples of the negative electrode active material
`according to the present invention include GeO, GeO, SnO,
`SiO, SnO, PbO, PbO2, PbO, PbO, SbO, SbO,
`Sb2O5, BiO3, BiO, and BiO, and non-stoichiometrical
`compounds of these oxides.
`Preferred of them are SnO, SnO, GeO, and GEO, with
`SnO and SnO, being particularly preferred. O-PbO-structure
`SnO, rutile-structure SnO2, GeO, and rutile-structure GeO,
`are preferred, with O-PbO-structure SnO and rutile-structure
`SnO, being particularly preferred.
`Still preferred negative electrode active materials are
`represented by formula (I):
`
`(I)
`M.M.M.
`wherein M' and M, which are different from each other,
`each represent at least one of Si, Ge, Sn, Pb, P, B, A, AS, and
`Sb, preferably at least one of Si, Ge, Sn, Pb, P, B, Al, and Sb,
`still preferably at least one of Si, Ge, Sn, Pb, P, B, and Al;
`M' represents at least one of O, S, Se, and Te, preferably at
`least one of O and S, still preferably O; p represents a
`number exceeding 0 and not exceeding 10, generally from
`0.001 to 10, preferably from 0.01 to 5, still preferably from
`0.01 to 2, and q represents a number of from 1 to 50,
`preferably 1 to 26, still preferably 1.02 to 6.
`Also, preferred are those of formula (I) in which M and
`M’ are different from each other; M' represents at least one
`of Ge, Sn, Pb, Sb, and Bi; M' represents at least one atom
`of the groups 13, 14, and 15 of the periodic table (exclusive
`of Ge, Sn, Pb, Sb, and Bi when M' represents each of these);
`prepresents a number of from 0.001 to 1; and M and q have
`the same meanings as defined in formula (I) above.
`The valency of M' or M' in formula (I) is not particularly
`limited and may be either a single valency or a mixed
`valency. The M' to M' ratio may vary continuously within
`a range of from more than 0 up to 10 molar equivalents. The
`amount of M', represented by q in formula (I), continuously
`varies accordingly.
`Of the compounds of formula (I), preferred are those in
`which M' is Sn, i.e., compounds represented by formula (II):
`SnM.M.,
`(II)
`wherein M represents at least one of Si, Ge, Pb, P, B, Al, As,
`and Sb, preferably at least one of Si, Ge, Pb, P, B, Al, and
`Sb, still preferably at least one of Si, Ge, Pb, P, B, and Al;
`M represents at least one of O and S, preferably O; p
`represents a number exceeding 0 and not exceeding 10,
`generally from 0.001 to 10, preferably from 0.01 to 5, more
`preferably a number of from 0.01 to 1.5, still preferably from
`0.7 to 1.5; and q represents a number of from 1.0 to 50,
`preferably from 1.0 to 26, still preferably from 1.02 to 6.
`Still preferred of the compounds represented by formula
`(II) are those represented by formula (III):
`
`(III)
`SnM.O.
`wherein M is as defined above, preferably Si; r represents
`a number of exceeding 0 and not exceeding 5.0, generally
`from 0.01 to 5.0, preferably a number of from 0.01 to 1.5,
`
`5,618,640
`
`5
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`Samsung Ex. 1023, Page 5 of 26
`Samsung Electronics Co., Ltd. v. RJ Technology, LLC
`IPR2023-01183
`
`

`

`Samsung Ex. 1023, Page 6 of 26
`Samsung Electronics Co., Ltd. v. RJ Technology, LLC
`IPR2023-01183
`
`

`

`7
`PbBO-5, PbSioGeo Oa,
`PbPO,
`PbSioGeo2O3,
`PbPogGeo. O3.45,
`PbSiosGeo-O3,
`PbPosGeo2O34,
`PbBosGeo2O26,
`PbBooCeo.1O2.65,
`PbPosGeo.50.325,
`PbCeoloSioO,
`PbCeoSio2O3,
`PbBosGeo.5027s,
`PbCeogPoiO305,
`PbCeogBo02.95.
`PbCeosPo2O3.1,
`PbSisO, PbCeO, PbPOs,
`PbCeosBoaO29,
`PbSiO, PbCeO, PbPO,
`PbB.O.s, PbCe2O3,
`GeSio.oO2.02, GeSioosO11,
`PbB2O5, GeSiolo Olo2,
`GeSiolos O21, GeSioli O12, GeSioO2.2, GeSio2O14,
`GeSio2O24,
`GeSioaC16,
`GeSioaC26,
`GeSio502,
`GeSiO, GeSiO, GeSio, Oa, GeSiO3, GeSiO,
`GeSi15O4, GeSii.50s, GePoo. Oozs, GePoo O2,025,
`GePoo.501.125, GePoo.502.125, GePo.1O12s, GePoiO2.25,
`GePo2O5, GePo2O2.s,
`GePoaO.7s,
`GePoaO27s,
`GePois0225, GePosO3.2s, GePoyO2.75, GePo/O37s,
`GePOs,
`GePOs,
`GeP504.75,
`GeP1.505.7s,
`GeBool Olois,
`GeBool Ozols,
`GeBoosoo75,
`GeBoosC2075, GeBo. O1.15, GeBo. 102.1s, GeBo2O3,
`GeBo2O2.3, GeBo.301.45, GeBoaO2.45, GeBos01.75,
`GeBosO2.75, GeBo7Ozos, GeBo/Osos, GeBO25, GeBO35,
`GeB1503.2s and GeB1s.O425.
`The use of any of the compounds represented by formulae
`(I) to (V) as a main negative electrode active material affords
`a nonaqueous secondary battery having excellent charge and
`discharge cycle characteristics, a high discharge potential, a
`high capacity and high safety.
`The pronouncedly excellent effects of the present inven
`tion come from the use of a compound containing Sn in
`which Sn is present with divalency. The valency of Sn can
`be determined through chemical titration, for example,
`according to the method described in Physics and Chemistry
`of Glasses, Vol. 8, No. 4, p. 165 (1967). It is also decided
`from the Knight shift in the solid nuclear magnetic reso
`nance spectrum of Sn. For example, in broad-line NMR
`measurement, metallic Sn (zero valent Sn) shows a peak in
`35
`an extremely low magnetic field in the vicinity of 7000 ppm
`with reference to Sn(CH), whereas the peak of SnO
`(divalent Sn) appears around 100 ppm, and that of SnO,
`(tetravalent Sn) appears around -600 ppm. Like this, the
`Knight shift largely depends on the valency of Sn, the center
`metal, with the ligands being the same. The valency can thus
`be determined by the peak position obtained by 'Sn-NMR
`analysis.
`The negative electrode active material of the present
`invention may contain various compounds, such as com
`45
`pounds of the group 1 elements (e.g., Li, Na, K, Rb, and Cs),
`transition metals (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn,
`Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, lanthanoid metals, Hf, Ta,
`W, Re, Os, Ir, Pt, Au, Hg), the group 2 elements (e.g., Be,
`Mg, Ca, Sr, Ba), and the group 17 elements (e.g., F, Cl, Br,
`50
`I). Further, it may also contain dopants of various com
`pounds (e.g., compounds of Sb, In, Nb) for improving
`electrical conductivity. The addition amount thereof is pref
`erably 0 to 20 mol%.
`The compounds of formulae (I) to (V) can be synthesized
`by either a calcination method or a solution method.
`For instance, the calcination method is conducted by
`calcining a mixed compound of M' compound and M
`compound (where M and M’, which are different from each
`other, each represent Si, Ge, Sn, Pb, P, B, Al, As, Sb).
`60
`The tin compounds include SnO, SnO, SnO, SnO,
`SnOHO, SnOs, stannous hydroxide, stannic oxyhy
`droxide, Stannic acid, stannous oxalate, Stannous phosphate,
`orthostannic acid, metastannic acid, parastannic acid, stan
`nous fluoride, Stannic fluoride, stannous chloride, Stannic
`chloride, stannous bromide, stannic bromide, stannous
`iodide, stannic iodide, tin selenide, tin telluride, stannous
`
`65
`
`25
`
`30
`
`40
`
`55
`
`5,618,640
`
`O
`
`15
`
`20
`
`8
`pyrophosphate, tin phosphite, Stannous Sulfate, Stannic Sul
`fate.
`The silicon compounds include SiO, SiO, organic silicon
`halide compounds such as silicon tetrachloride, silicon,
`tetrafluoride, trichloromethylsilane, dimethyldichlorosilane
`and tetraethhylsilane, alkoxysilance compounds such as
`tetramethoxysilane and tetraethoxysilane, and hydroxysi
`lane compounds such as trichlorohydroxysilane.
`The germanium compounds include GeO2, GeO, germa
`nium tetrachloride, and alkoxy germanium compounds such
`as germanium tetramethoxide and germanium tetraethoxide.
`The lead compounds include PbO2, etc. 203, PbO4,
`PbCl, lead chlorate, lead perchlorate, lead nitrate, lead
`carbonate, lead formate, lead acetate, lead tetraacetate, lead
`tartrate, lead diethoxide, lead di(isopropoxide).
`The phosphorus compound includes phosphorus pentox
`ide, phosphorus oxychloride, phosphorous pentachloride,
`phosphorus trichloride, phosphorous tribromide, trimethyl
`phosphate, triethyl phosphate, tripropyl phosphate, stannous
`pyrophosphate, and boron phosphate.
`The boron compound includes boron sesquioxide, boron
`trichloride, boron tribromide, boron carbide, boric acid,
`trimethyl borate, triethyl borate, tripropyl borate, tributyl
`borate, boron phosphide, and boron phosphate.
`The aluminum compound includes aluminum oxide
`(O-alumina or f3-alumina), aluminum silicate, aluminum
`triisopropoxide, aluminum tellurite, aluminum chloride, alu
`minum boride, aluminum phosphide, aluminum phosphate,
`aluminum lactate, aluminum borate, aluminum sulfide, and
`aluminum sulfate.
`The antimony compound includes antimony tribromide,
`antimony trichloride, diantimony trioxide, and triphenylan
`timony.
`Calcination is carried out preferably at a rate of tempera
`ture rise of 4° to 2000° C./min, still preferably 6° to 2000
`C./min, most preferably 10° to 2000°C/min: at a calcina
`tion temperature of 250° to 1500° C., still preferably 350° to
`1500° C., most preferably 500 to 1500° C.; for a period of
`0.01 to 100 hours, still preferably 0.5 to 70 hours, most
`preferably 1 to 20 hours. After calcination, the system is
`cooled at a rate of temperature drop of 2° to 107°C/min, still
`preferably 4 to 10°C/min, still more preferably 6° to 107
`C./min, most preferably 10° to 10°C/min.
`The term “rate of temperature rise' as used herein means
`an average rate of temperature rise from 50% calcination
`temperature (C) up to 80% calcination temperature (C.),
`and the term "rate of temperature drop' as used herein
`means an average rate of temperature drop from 80%
`calcination temperature (C.) to 50% calcination tempera
`ture (C.).
`Cooling of the calcined product may be effected either
`within a calcining furnace or out of the furnace, for example,
`by pouring the product into water. Super-quenching methods
`described in Ceramics Processing, p. 217, Gihodo (1987),
`such as a gun method, a Hammer-Anvil method, a slap
`method, a gas atomizing method, a plasma spray method, a
`centrifugal quenching method, and a melt drag method, can
`also be used. Further, cooling may be conducted by a single
`roller method or a twin-roller method described in New
`Glass Handbook, p. 172, Maruzen (1991). Where the mate
`rial melts during calcination, the calcined product may be
`withdrawn continuously while feeing the raw materials. The
`molten liquid is preferably stirred during calcination.
`The calcining atmosphere preferably has an oxygen con
`tent of not more than 100% by volume, preferably not more
`than 20% by volume, more preferably not more than 5% by
`volume. An inert gas atmosphere is still preferred. Inert gas
`includes nitrogen, argon, helium, krypton, and xenon.
`
`Samsung Ex. 1023, Page 7 of 26
`Samsung Electronics Co., Ltd. v. RJ Technology, LLC
`IPR2023-01183
`
`

`

`5,618,640
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`9
`The compound of formulae (I) to (V) preferably has an
`average particle size of from 0.1 to 60 lum. The calcined
`product can be ground to size by means of well-known
`grinding machines or classifiers, such as a mortar, a ball mill,
`a Sand mill, a vibration ball mill, a satellite ball mill, a
`planetary ball mill, a spinning air flow type jet mill, and a
`sieve. If necessary, wet grinding using water or an organic
`solvent, such as methanol, may be conducted. The grinds are
`preferably classified to obtain a desired particle size either
`by dry or wet classification by means of a sieve, an air
`classifier, etc.
`According to one of the embodiments of the present
`invention in which the negative electrode active material is
`an oxide containing fluorine, the fluorine in the negative
`electrode active material strengthens the structure and
`chemical stability of a compound oxide. In particular, fluo
`rine in an amorphous oxide is effective to further enhance
`the amorphous properties thereby improving the electro
`chemical structural stability.
`Specific examples of the fluorine-containing negative
`electrode active material or a precursor thereof are
`GeFo2Oo.9,
`GeFoC19,
`SnFo2O09,
`SnFo2O19,
`SnSiFoos, PbFoO, PbFo2O1.9,
`Pb2Fo2O29,
`Pb3Fo4O38,
`Sb2Fo2O29, Sb2Fo2O39,
`Sb2Fo2O49,
`Bi2Fo,038, Bi2FoC38, and BiFo209, and non-stoichio
`metrical compounds or compound oxides thereof.
`Preferred of these fluorine-containing negative electrode
`active materials are fluorine-containing SnO, SnO, GeO,
`GeO2, and SnSiO, with fluorine-containing SnSiO, being
`still preferred. Fluorine-containing and amorphous SnO,
`SnO, GeO, GeO, and SnSiO, are particularly preferred.
`A preferred fluorine content in the fluorine-containing
`negative electrode active material is from 10 to 100 mol %,
`particularly 20 to 50 mol %, based on the total amount of the
`metal elements in the active material.
`The F-containing negative electrode active materials pref
`erably include those represented by formula Sn,SiF.O.
`(0.2<Xs 1.0; 0<ys2; 2.2<zs3). The F-containing com
`pound oxide may be crystalline or amorphous but is pref
`erably amorphous.
`The F-containing negative electrode active material pre
`cursor mainly comprising Sn can be synthesized by calcin
`ing a mixture of the above-mentioned tin oxide and fluorine
`compound in air or an inert gas at a high temperature.
`In the case of adding another metal or metals, a mixture
`of the tin compound, the fluorine compound, and an oxide of
`another metal or metals is calcined. For example, fluorine
`containing SnSiO can be synthesized by calcining a mix
`ture of SnO, SnF, and SiO, in an inert gas at 200° to 1200°
`C., preferably 500 to 1100° C.
`For obtaining an amorphous (glassy) active material, the
`calcined product is quenched at a cooling rate of 1.5 to 100°
`C./min, preferably 5° to 20°C/min.
`The fluorine-containing negative electrode active material
`precursor can also be synthesized by co-precipitation in a
`solution (co-precipitation method). In this case, an acidic or
`alkaline aqueous Solution containing, for example a salt of
`the group 13, 14 or 15 element is neutralized in the presence
`of a fluoride ion to form a fluorine-containing compound
`hydroxide or a fluorine-containing compound oxide.
`The negative electrode active material precursors contain
`ing other metals can also be synthesized by the above
`described calcination method or co-precipitation method.
`The positive electrode active material which can be used
`in the present invention may be a transition metal oxide
`capable of reversibly intercalating and deintercalating a
`lithium ion but is preferably a lithium-containing transition
`metal oxide.
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`10
`Lithium-containing transition metal oxides which can be
`used as a positive electrode active material include, for
`preference, lithium-containing oxides of Ti, V, Cr, Mn, Fe,
`Co, Ni, Cu, Mo or W. The oxide may contain other alkali
`metals (the group 1 and 2 elements) in addition to Li and/or
`other elements such as Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P.
`B, etc. The ratio of these additional elements is preferably up
`to 30 mol %, still preferably up to 10 mol %, based on the
`transition metal.
`Preferred of the Li-containing transition metal oxides as a
`positive electrode active material are those prepared from a
`mixture of a lithium compound and at least one compound
`of a transition metal selected from Ti, V, Cr, Mn, Fe, Co, Ni,
`Mo, and W at a lithium compound/total transition metal
`compounds molar ratio of 0.3 to 2.2.
`Still preferred are those prepared from a mixture of a
`lithium compound and at least one compound of a transition
`metal selected from V, Cr, Mn, Fe, Co, and Ni at a lithium
`compound/total transition metal compounds molar ratio of
`from 0.3 to 2.2.
`The most preferred are those represented by formula
`LiQO, (Q represents at least one transition metal selected
`from Co, Mn, Ni, V, and Fe; x is from 0.2 to 1.2; and y is
`from 1.4 to 3). Q may contain, in addition to a transition
`metal, other metals, such as Al, Ga, In, Ge, Sn, Pb, Sb, Bi,
`Si, P, B, etc. The ratio of the other metals is preferably up to
`30 mol % based on the total transition metals.
`Suitable examples of the lithium-containing metal oxide
`positive electrode active material which can be preferably
`used in the present invention are LiCoO, LiNiO,
`LiMnO2, LiCONiO2, LiCo.V.O., LiCoFe O2,
`LiMn2O4, LiMnCo-Oa, Li Min Ni2O, LiMnV
`cO, LiMnFe2O, a mixture of LiMnO, and MnO, a
`mixture of LiMnO and MnO, a mixture of LiMn2O,
`LiMnO, and MnO, (wherein x=0.2 to 1.2; a=0.1 to 0.9;
`b=0.8 to 0.98; c=1.6 to 1.96; and Z=2.01 to 5).
`Preferred examples of the lithium-containing metal oxide
`positive electrode active materials are LiCoO, LiNiO,
`LiMnO2, LiCo.NiO2, Li,CO.V. O., Li CoFe-O2.
`LiMn2O4, LiMn-Co2O4, LiMnNi2O, LiMnV2
`cO, and LiMnFe O (wherein x=0.7 to 1.2; a-0.1 to 0.9;
`b=0.8 to 0.98; c=1.6 to 1.96; Z=2.01 to 2.3).
`Still preferred of the lithium-containing metal oxide posi
`tive electrode active materials are LiCoO, LiNiO,
`LiMnO2, LiCoNiO2, LiMn2O4, and LiCo.V.O.
`(wherein x=0.7 to 1.2; a-0.1 to 0.9; b=0.9 to 0.98; and
`Z=2.01 to 2.3).
`The most preferred are LiCoO, LiNiO2, LiMnO,
`LiCo.NiO2, LiMn2O4, and LiCo.V.O. (wherein
`x=0.7 to 1.2: a-0.1 to 0.9; b=0.9 to 0.98; and Z-2.02 to 2.3).
`The value x in the above formulae is the value before
`commencement of charging and discharging and varies with
`a charge and a discharge.
`According to another embodiment of the present inven
`tion, a spinel type manganese-containing oxide is used as a
`positive electrode active material. Spinel type oxides have a
`spinel structure represented by formula A(B)O, in which
`the oxygen anions are aligned in cubic closest packing and
`occupy part of the faces and apexes of a tetrahedron and an
`octahedron. The unit cell is composed of 8 molecules, a