fl TRANSPERFECT
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`I, Benjamin Ettinger, hereby certify that I am competent to translate from Japanese to English
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`and that the attached translation is, to the best of my knowledge and belief, a true and accurate
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`translation of the document entitled from Japanese to English.
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`"Yasunami"
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`•
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`� .
`��
`�
`� �
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`
`Benjamin Ettinger
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`Sworn to before me this
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`November 27, 2023
`
`AKASH SABLOK
`
`A Notary Public
`in and for t�e
`Province of British
`Columbia
`610s Fraser Street, Vancouver,
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`Canada V5W 3A1 www.sablok.com
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`Stamp, Notary Public
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`LANGUAGE AND TECHNOLOGY SOLUTIONS FOR GLOBAL BUSINESS
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`
`RJ Technology Exhibit 2001
`Apple Inc. v. RJ Technology LLC
`IPR2023-01350, Page 1 of 34
`
`

`

`RJ Technology Exhibit 2001
`Apple Inc. v. RJ Technology LLC
`IPR2023-01350, Page 2 of 34
`
`

`

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`(12)Japanese Unexamined Patent
`
`(11) Japanese Unexamined Patent
`(19)Japan Patent Office (JP)
`Application Publication Number
`
`Application Publication
`(A)
`H7-122298
`
`(43) Publication date: May 12, 1995
`
`Identification codes
`
`JPO file numbers
`FI
`
`
`
`Technical indications
`
`(51)Int. Cl.6
`HOlM 10/40
`4/58
`10/44
`
`z
`
`z
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`
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`
`
`
`
`
`
`Request for examination: Not yet requested Number of claims: 9 OL (Total
`of 15 pages)
`
`(21)Application number
`
`
`
`Japanese Patent (71) Applicant
`000005201
`Application
`
`FUJIFILM Corporation
`
`
`210 Nakanuma, Minamiashigara-shi, Kanagawa­
`H5-263696
`ken
`
`(22)Date of application
`
`October 21, 1993
`
`(72)Inventor
`
`Shoichiro y ASUNAMI
`
`
`c/o FUJIFILM Corporation
`
`
`210 Nakanuma, Minamiashigara-shi, Kanagawa­
`ken
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`
`
`(54)(TITLE OF THE INVENTION) METHOD FOR CHARGING AND DISCHARGING A NON-AQUEOUS SECONDARY
`
`
`
`
`BATTERY
`
`(57)(ABSTRACT)
`(PROBLEM) Provide a non-aqueous secondary battery
`
`
`
`
`
`having a large discharge capacity, a high discharge
`
`
`
`operating voltage, and good charge/discharge cycle
`
`
`characteristics, and a method for charging and discharging
`the same.
`(MEANS FOR SOLVING) Non-aqueous secondary battery that
`
`
`
`
`
`
`adopts a method whereby charging is performed after
`
`discharging to 0.5 to 1.5 V during the charge/discharge
`
`
`
`cycle of a non-aqueous secondary battery in which the
`
`
`
`
`negative electrode active material is a lithium-containing
`
`
`transition metal oxide represented by LixMOj (where M
`
`
`represents at least one type of transition metal selected
`from among Ti, V, Mn, Co, Fe, Ni, Nb, and Mo, x is within
`
`the range of 1.6the range of 0.17 to 11.25, and j is within
`
`
`
`
`
`to 4.1), the positive electrode active material is a lithium­
`by LiyNO,
`
`
`containing transition metal oxide represented
`
`
`(where N represents at least one type of transition metal,
`
`
`
`and at least one type of these transition metals represents at
`
`
`least one type of transition metal selected from among Co,
`
`Mn, Ni, V, and Fe, y is within the range of 0.2 to 1.2, and z
`is within the range of 1.4 to 3), and the end-of-charge
`
`voltage is set to 3.5 to 4.7 V.
`
`RJ Technology Exhibit 2001
`Apple Inc. v. RJ Technology LLC
`IPR2023-01350, Page 3 of 34
`
`

`

`
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`
`
`Japanese Unexamined Patent Application Publication H7-l 22298
`
`
`
`
`
`(2)
`
`LiyCoaNi1-aO2,
`LiyCObFe1-bO2, LiyMil2O4,
`
`LiyCObV1-bO2,
`(SCOPE OF PATENT CLAIMS)
`
`
`LiyMncC02-cO4, LiyMncNi2-cO4,
`(CLAIM 1) Method for charging and discharging a non­
`
`
`LiyMncV2-cO4,
`and
`
`
`the range of 0.5 to 1.2, a LiyMncFe2-cO4 (where y is within
`
`
`aqueous secondary battery compnsmg non-aqueous
`
`
`is within the range of 0.1 to 0.9, b is within the range of0.8
`
`
`
`
`
`electrolyte containing positive electrode active material,
`
`to 0.98, c is within the range of 1.6 to 1.96, and z is within
`
`
`
`
`
`negative electrode active material, and lithium chloride,
`the range of 2.01 to 2.3).
`
`
`
`
`
`wherein said negative electrode active material is a lithium­
`
`
`(DETAILED DESCRIPTION OF THE INVENTION)
`
`
`
`containing transition metal oxide represented by LixMOj
`(0001)
`
`
`(where M represents at least one type of transition metal
`(FIELD OF INDUSTRIAL APPLICATION) The present invention
`
`
`
`
`selected from among Ti, V, Mn, Co, Fe, Ni, Nb, and Mo, x
`
`
`
`relates to a method for charging and discharging a non­
`
`
`is within the range of 0.17 to 11.25, and j is within the
`
`
`
`
`aqueous secondary battery with improved charge/discharge
`
`
`range of 1.6 to 4.1), and said positive electrode active
`cycle characteristics.
`
`
`
`material is a lithium-containing transition metal oxide
`(0002)
`
`represented by LiyNOz (where N represents
`at least one
`(PRIOR ART) Lithium metal and lithium alloy are
`
`
`
`type of transition metal, and at least one type of these
`
`
`
`representative examples of materials that can be used as the
`
`
`transition metals represents at least one type of transition
`
`
`
`
`negative electrode material of a non-aqueous secondary
`
`metal selected from among Co, Mn, Ni, V, and Fe, y is
`
`
`
`
`battery lithium. However, a problem with the same is that
`
`
`within the range of 0.2 to 1.2, and z is within the range of
`
`when these are used, the lithium metal grows dendritically
`
`
`
`1 .4 to 3 ), characterized in that the end-of-charge voltage is
`
`
`during charging and discharging, which poses the risk of
`
`3.5 to 4.7 V, and, during the charge/discharge cycle,
`
`
`
`internal shorting as well as posing the risk of fire due to the
`
`
`
`charging is performed after discharging to 0.5 to 1.5 V.
`
`
`
`fact that the dendritic metal itself is highly active. To
`
`
`(CLAIM 2) Method for charging and discharging a non­
`
`
`combat this, fired carbonaceous materials have recently
`
`
`aqueous secondary battery set forth in claim 1,
`
`
`
`been developed that are able to absorb and release lithium.
`
`characterized in that the range for the end-of-discharge
`
`
`These carbonaceous materials proffer numerous
`
`
`voltage that is used is 1.5 V or greater and 3 .0 V or less.
`
`
`
`
`advantages, including relatively low risk of igniting, high
`
`
`(CLAIM 3) Method for charging and discharging a non­
`
`
`
`
`charge/discharge capacity, etc. However, a drawback is
`
`
`aqueous secondary battery set forth in claim 1,
`
`
`
`
`that, because the material itself is conductive, overcharging
`
`characterized in that the range for the end-of-discharge
`
`
`or rapid charging can cause lithium metal to precipitate
`
`
`voltage that is used is 0.5 V or greater and less than 1.5 V.
`
`
`
`onto the carbonaceous material, again leading to dendritic
`
`
`(CLAIM 4) Method for charging and discharging a non­
`
`
`metal precipitation. A variety of methods have been
`
`
`
`aqueous secondary battery set forth in claim 1, wherein said
`
`
`
`
`adopted to avoid this, including modifying the charger or
`
`
`
`
`negative electrode active material is a transition metal
`
`
`
`
`
`reducing the amount of positive electrode active material so
`
`
`
`oxide wherein the basic structure of the crystal is changed
`
`
`
`
`as to prevent overcharging. However, a problem with the
`
`
`
`by insertion of lithium ions, and the changed basic structure
`
`
`
`latter method is that limiting the amount of active material
`
`
`
`
`of the crystal is not subsequently changed by charging and
`
`
`
`
`material [sic] also winds up limiting the discharge capacity.
`discharging.
`
`
`
`Furthermore, due to the fact that carbonaceous material has
`(CLAIM 5) Non-aqueous secondary battery set forth in claim
`
`
`
`
`
`
`a relatively low density, the latter method also winds up
`
`
`
`1, wherein said transition metal oxide prior to insertion of
`
`
`having a low discharge capacity per unit volume.
`
`
`
`aid lithium ions is a transition metal oxide represented by
`
`
`
`
`Consequently, discharge capacity ends up being limited in
`
`LipMOj (where M represents at least one type of transition
`
`
`two ways: limited amount of active material and low
`
`metal selected from among Ti, V, Mn, Co, Fe, Ni, Cr, Nb,
`
`capacity per unit volume.
`
`
`and Mo, p is within the range of O to 3.1, and j is within the
`(0003) In contrast, other than lithium metal, lithium alloy,
`
`
`
`
`
`range of 1.6 to 4.1).
`
`
`and carbonaceous material, other types of negative
`(CLAIM 6) Non-aqueous secondary battery set forth in claim
`
`
`
`
`
`
`electrode active materials that are known include: TiS2 and
`
`
`
`1 or 2, wherein said negative electrode material is an oxide
`
`
`
`LiTiS2, which are able to absorb and release lithium ions
`
`
`of transition metal wherein lithium ions have been
`
`(U.S. Patent No. 3,983,476), WO2, which has a rutile
`
`electrochemically inserted.
`
`
`strncnlfe (U.S. Patent No. 4,198,476), spine! compounds
`(CLAIM 7) Method for charging and discharging a non­
`
`
`
`
`
`such as LixFe(Fe2)O4, etc. (Japanese Unexamined Patent
`
`
`
`aqueous secondary battery set forth in claim 1, wherein said
`
`
`
`Application Publication S58-220362), electrochemically
`
`
`
`
`negative electrode material is obtained by further inserting
`
`
`
`
`synthesized lithium compounds of Fe2O3 (U.S. Patent No.
`
`
`lithium ions into a lithium-containing transition metal oxide
`
`
`
`4,464,447), lithium compounds of Fe2O3 (JUPAP H3-
`
`produced by firing.
`
`
`
`112070), Nb2Os (Japanese Examined Patent Application
`(CLAIM 8) Method for charging and discharging a non­
`
`
`
`
`
`Publication S62-59412, JUPAP H2-82447), iron oxide,
`
`
`
`
`aqueous secondary battery set forth in claim 1, wherein said
`
`
`
`
`FeO, Fe2O3, Fe3Q4, cobalt oxide, CoO, Co2O3, and Co3Q4
`
`
`
`negative electrode material is a lithium-containing
`(JUPAP H3-291863).
`
`
`
`transition metal oxide represented by LixMqV1-qOj (where
`
`
`
`
`M represents a transition metal, p is within the range of O to
`
`
`
`3.1, x is within the range of 0.17 to 11.25, q is within the
`
`range ofO to 0.7, and j is within the range of 1.3 to 4.1).
`
`
`(CLAIM 9) Method for charging and discharging a non­
`
`
`
`
`aqueous secondary battery set forth in claim 1, wherein said
`
`
`
`
`positive electrode active material is a lithium-containing
`by LiyCoO2, LiyNiO2,
`
`transition metal oxide represented
`
`RJ Technology Exhibit 2001
`Apple Inc. v. RJ Technology LLC
`IPR2023-01350, Page 4 of 34
`
`

`

`
`
`
`
`Japanese Unexamined Patent Application Publication H7-122298
`
`
`
`(3)
`
`(0008) For the purposes of the present invention, transition
`
`
`
`
`(0004) Furthermore, examples of known combinations of
`
`
`
`
`
`
`
`metals include element number 21 (Sc) to element number
`
`
`
`
`positive electrode materials and negative electrode
`
`
`30 (Zn), element number 39 (Y) to element number 48
`
`
`
`materials that are metal chalcogenides include: TiS2 and
`
`
`(Cd), and element number 57 (La) to element number 80
`
`
`
`LiTiS2 (U.S. Patent No. 983,476), chemically synthesized
`(Hg).
`
`Li0.l V2Os and LiMnl-sMesO2 (0.1 < s < 1, Me= transition
`(0009) The non-aqueous secondary battery of the present
`
`
`
`
`
`metal; JUPAP S63-210028), chemically synthesized
`
`
`
`invention has a basic structure comprising positive
`
`
`Lio.1V2Oo.1 and LiC01-sFesO2 (s = 0.05 to 0.3; JUPAP S63-
`
`
`
`
`electrode active material, negative electrode active
`
`
`
`
`211564), chemically synthesized Lio.1V2Os and LiC01-
`
`
`
`
`material, and non-aqueous electrolyte containing lithium
`
`sNisO2 (s = 0.5 to 0.9; JUPAP H l-294364), V2Os and
`
`
`
`
`
`
`salt. The aforesaid negative electrode active material can be
`
`
`Nb2Os + lithium metal (JUPAP H2-82447), V2Os or TiS2
`
`
`
`either a transition metal oxide that may contain lithium or a
`
`
`
`and electrochemically synthesized LixFe2O3 (U.S. Patent
`
`
`
`
`material obtained by inserting lithium ions into this
`
`
`No. 4,464,447; Journal of Power Sources, Vol. 8, p. 289,
`
`
`
`transition metal oxide, and is preferably obtained by
`
`
`1982), LiNixC01-xO2 for both the positive electrode active
`
`
`inserting lithium ions into a transition metal oxide
`
`
`
`
`
`material and the negative electrode active material (0 :S x <
`
`containing lithium (preferably by electrochemical
`
`
`1; JUPAP Hl-120765; in the specification, the embodiment
`insertion).
`
`
`
`
`examples state that the positive electrode active material
`
`(0010) The transition metal oxide used in the present
`
`
`
`
`and the negative electrode active material are the same
`
`
`
`
`invention prior to insertion of lithium ions (referred to
`
`compound), LiCoO2 or LiMnzQ4 and iron oxide, FeO,
`
`
`
`hereafter as the negative electrode active material
`
`
`
`
`Fe2O3, Fe3Q4, cobalt oxide, CoO, Co2O3, or Co3Q4 (JUP AP
`
`
`
`precursor) is preferably synthesized by mixing two or more
`
`H3-291863), etc.
`
`
`
`
`types of transition metal compounds in the desired ratio, or
`(0005) Among these, the best candidate in terms of being
`
`
`
`
`by mixing a lithium compound and one or more type of
`
`
`
`
`the aforesaid negative electrode active material that
`
`
`transition metal compound in such a way that the molar
`
`
`
`exhibits high safety, high discharge capacity, and high
`
`
`ratio of lithium compound to total transition metal
`
`
`
`
`battery voltage (3 V rating) is a non-aqueous secondary
`
`
`
`
`compound attains no greater than 3.1. However, transition
`
`
`
`battery using lithium-containing transition metal oxide as
`
`
`
`metal refers to a transition metal including at least one type
`
`
`
`
`the negative electrode active material. However, a major
`among Ti, V, Mn, Co, Ni, Fe, Cr, Nb, and Mo.
`
`
`
`
`hurdle preventing development of this material is the fact
`
`
`
`Furthermore, the aforesaid negative electrode active
`
`
`that it exhibits poor cycle characteristics, which has led to
`
`
`
`
`material precursor is preferably synthesized by mixing the
`
`strong demand for the improvement of its cycle
`
`
`
`lithium compound and the transition metal compound in
`characteristics.
`
`
`such a way that the molar ratio of lithium compound to
`(0006)
`
`
`
`total transition metal compound attains 0.2 to 3.1. For the
`(PROBLEM TO BE SOLVED BY THE INVENTION) The objective
`
`
`
`
`
`
`purposes here, transition metal refers to a transition metal
`
`
`
`of the present invention is to provide a non-aqueous
`
`including at least one type among Ti, V, Mn, Co, Ni, and
`
`
`
`
`secondary battery having a high battery voltage, a high
`Fe.
`
`
`
`discharge capacity (high energy density), and a long
`(0011) At least one type of transition metal oxide serving as
`
`
`
`
`
`charge/discharge cycle lifespan, and a method for charging
`
`
`
`
`
`a negative electrode active material precursor in the present
`
`and discharging the same.
`
`
`
`invention is represented by LipMOj (where M represents at
`(0007)
`
`
`least one type of transition metal, and at least one type of
`(MEANS FOR SOLVING THE PROBLEM) The aforesaid
`
`
`
`this transition metal is selected from among Ti, V, Mn, Co,
`
`
`
`
`objective is achieved by charging after discharging to 0.5 to
`
`Ni, Fe, Cr, Nb, and Mo, p is within the range of Oto 3.1,
`
`
`1.5 V during the charge/discharge cycle of a non-aqueous
`
`and j is within the range of 1.6 to 4.1 ).
`
`
`
`
`secondary battery in which the negative electrode active
`(0012) The aforesaid negative electrode active material
`
`
`
`
`
`
`
`material is a lithium-containing transition metal oxide
`
`
`
`precursor is furthermore preferably LipM1qlM2q2 ...
`
`
`represented by LixMOj (where M represents at least one
`
`MnqnOj (where M1M2 ... Mn each represent said transition
`
`
`type of transition metal selected from among Ti, V, Mn,
`
`
`metal, at least one of which represents Ti, V, Mn, Co, Ni,
`
`Co, Fe, Ni, Nb, and Mo, x is within the range of 0.17 to
`
`or Fe, p is within the range ofO to 3.1, q l+q2+ ... +qn = 1, n
`
`
`11.25, and j is within the range of 1.6 to 4.1), the positive
`
`
`is within the range of 1 to 10, and j is within the range of
`
`
`
`
`electrode active material is a lithium-containing transition
`
`
`
`1.6 to 4.1). Furthermore, in the aforesaid formula, it is even
`
`by LiyNOz (where N represents at
`metal oxide represented
`
`
`more preferred that p is within the range of 0.2 to 3.1, n is
`
`
`
`least one type of transition metal, and at least one type of
`
`
`within the range of 1 to 4, andj is within the range of 1.8 to
`
`
`these transition metals represents at least one type of
`
`
`
`4.1. It is particularly preferred, in the aforesaid formula,
`
`
`transition metal selected from among Co, Mn, Ni, V, and
`
`
`that p is within the range of 0.2 to 3.1, n is within the range
`
`
`Fe, y is within the range of 0.2 to 1.2, and z is within the
`
`of 1 to 3, and j is within the range of 1.8 to 4.1.
`
`
`range of 1.4 to 3), and the end-of-charge voltage is set to
`
`
`
`(0013) It is advantageous toward the aim of achieving high
`3.5 to 4.7 V.
`
`
`
`
`discharge capacity for the negative electrode active
`
`
`
`
`
`material precursor of the present invention to include at
`
`least one or more types of transition metals in which a
`
`
`
`
`valence of 5+ to 6+ is stably present, as described above
`
`(for example, V, Cr, Nb, or Mo).
`
`RJ Technology Exhibit 2001
`Apple Inc. v. RJ Technology LLC
`IPR2023-01350, Page 5 of 34
`
`

`

`
`
`
`
`Japanese Unexamined Patent Application Publication H7-l 22298
`
`
`
`
`
`(4)
`
`LiNio.2Cdo.3 V o.sO2.1,
`
`(0014) The aforesaid negative electrode active material
`
`
`
`
`Li Coo.2sCeo.25 V o.sO2.2,
`
`
`
`
`precursor containing V, etc. is preferably LipM1qlM2q2 ...
`
`
`
`Li1,03Coo.2Smo.3 Vo.sO2.1, Lio.ssNao.1sCoo.4Geo.2 V 0.4O2.1. Note
`
`
`that the stoichiometric coefficient for oxygen is obtained
`
`
`
`MnqnXqvOj (where M is a transition metal, X is V, Cr, Nb,
`
`
`from the weight of the compound prior to firing and the
`
`
`or Mo, p is within the range of Oto 3.1, ql + q2 + ... + qn
`
`
`
`weight of the compound after firing. For this reason, it is
`
`
`+qv = 1, n is within the range of 1 to 9, and j is within the
`
`
`necessary to factor in an error of -10 to 10% of the
`
`range of 1.3 to 4.1). Furthermore, toward the aim of
`
`
`
`aforesaid value for the stoichiometric coefficient for
`
`
`
`achieving high discharge capacity, it is particularly
`
`
`oxygen in order to account for the precision of the
`
`
`
`preferred that these negative electrode active material
`
`measurement method.
`
`
`
`precursors include at least V. It is even more preferred that
`(0017) The negative electrode active material of the present
`
`
`
`
`
`
`
`
`
`
`the aforesaid negative electrode active material precursor
`
`
`
`
`invention comprises the aforesaid negative electrode active
`
`
`including V is LipMqlMq2Vt-(ql+q2)Oj (where M is a
`
`
`
`material precursor into which lithium ions have been
`
`
`
`transition metal, p is within the range of 0.2 to 3.1, ql + q 2
`
`
`
`inserted. Accordingly, the transition metal oxide of the
`
`
`the range ofi s within the range o f Oto 0.7, and j i s within
`
`
`
`
`
`
`aforesaid negative electrode active material precursor that
`
`
`1.3 to 4.1). It is most preferred that the aforesaid negative
`
`
`
`
`may contain lithium, or Lip, becomes Lix. In short, x is
`
`
`
`
`electrode active material precursor including V is
`
`
`
`generally within the range of 0.17 to 11.25 (the amount of
`
`
`
`LipCoqV1-qOj, LipNiqV1-qOj (where p is within the range
`
`
`
`
`increase of lithium due to insertion of lithium ions, or x-p,
`
`of 0.3 to 2.2, q is within the range of 0.02 to 0.7, and j is
`
`
`is generally within the range of 0.17 to 8.15). For example,
`
`within the range of 1.5 to 2.5).
`
`
`
`
`the negative electrode active material used in the present
`
`(0015) LipCoVO4 and LipNiVO4 (where p is within the
`
`
`
`
`invention, which is obtained by inserting lithium ions into
`
`range of 0.3 to 2.2) can be cited as particularly preferred
`
`
`LipMOj, which serves as the aforesaid preferred negative
`
`
`
`examples of the negative electrode active material
`
`
`
`electrode active material precursor, comprises at least one
`
`
`
`
`precursor of the present invention. Here, the aforesaid p
`
`
`type of lithium-containing trans1t1on metal oxide
`
`
`value is the value prior to starting charging and discharging,
`
`
`represented by LixMOj (where M represents at least one
`
`
`
`which is increased or decreased by charging and
`
`type of transition metal and at least one type of transition
`
`
`
`
`discharging. Furthermore, the negative electrode active
`
`metal is selected from among Ti, V, Mn, Co, Fe, Ni, Nb,
`
`
`
`
`material consists of this precursor compositional formula
`
`and Mo, p is within the range of 0 to 3.1, x is within the
`
`
`
`
`with additional lithium content. Because the total transition
`
`
`range of 0.17 to 11.25, and j is within the range of 1.6 to
`
`
`
`metal M in the general formulae indicated in the present
`
`
`4.1). x is preferably within the range of 0.26 to 10.2, and x
`
`
`invention (for example, LipMOj) is set to 1, in the event
`
`
`is even more preferably within the range of 0.34 to 9.3. The
`
`
`
`
`
`that a plurality of transition metals should be included, or if
`
`
`
`
`
`
`preferred negative electrode active material comprises at
`
`
`
`using a crystallographic compositional formula, this
`
`
`
`least one type of transition metal oxide represented by
`
`
`number can be multiplied by the appropriate integer.
`
`
`
`
`LixMqV1-qOj (where M represents a transition metal, p is
`
`
`(0016) Specific examples of the most preferred negative
`
`
`within the range of Oto 3.1, x is within the range of 0.17 to
`
`
`
`
`
`electrode active material precursors will be cited below, but
`
`
`8.15, q is within the range of Oto 0.7, and j is within the
`
`
`
`
`the present invention is not limited to these. For example,
`LiCoo.5Vo.5O2.1,
`
`range of 1.3 to 4.1). x is preferably within the aforesaid
`
`
`LiVO3,1, LiTiO2.3, CoVO3.7, LiCoVO4,
`range.
`
`LiNiVO4.0, Li0,75Nio.5 Vo.5O2.1 , Li 1.75Nio.5
`Vo.5O2.4,
`(0018) The negative electrode active material of the present
`
`
`
`
`
`
`
`LiTio.5 Vo.5O2.9, LiMno.5 Vo.5O2.5, LiFeo,5Mno,5O2. L,
`
`
`
`
`
`invention is preferably obtained by inserting lithium ions
`
`
`
`LiCoo.25 V 0.15O2.s, LiNio.25Vo.15O2.s, LiNio.05Vo.95O3.1,
`
`
`
`into the transition metal oxide and/or the lithium-containing
`
`
`
`
`LiFeo.05 Vo.95O3. L, LiMno.05 Vo.95O3.o, LiCao.05 Vo.95O3.2,
`
`
`
`transition metal oxide serving as the negative electrode
`LiCoo.15Vo.25O1.9, LiMno.25Tio.s V 0.25O2.6, LiCro.05 Vo.95O3.2,
`
`
`
`LiNbo.05 V o.95O3. 1, LiMoo.05 V o.95O3.o, Lio.sN ao.2Coo.s V o.5O2. L,
`
`
`
`
`active material precursor in the manner described below.
`
`
`For example, the preferred method is to react with lithium
`
`
`V o.5O2.2,Lio_95Rbo.05N io.5 V 0.502.2, Lio.9Ko.2Coo.5
`
`
`
`lithium alloy, butyl lithium, or the like, or to insert
`metal,
`
`
`
`Lio.s5B ao.15Nio.5 V o.5O2.2, Lio.9COo.4A 1 0. 1 V o.5O2.1,
`
`
`
`
`lilhium ions eleclrud1emically. In Lile presenl invention, it
`Li Coo.45 G a o.as Vo. sO2. 2, Lio.9N i o . 2I no. 3 V o .5O2.3 ,
`
`
`
`
`is particularly preferred that lithium ions are inserted
`L i 1 .o s C o o.4T 1 o . 1 V o .sO2. 3 , L i 1.0 3G e o .5 Vo.5O2 . 3 ,
`
`
`
`
`electrochemically into the transition metal oxide serving as
`
`1,Lio.9sCoo.2sP b o . 2s Vo.sO2. 1, LiCoo.5Bio.s Vo.4sO2.
`
`
`
`
`
`the negative electrode active material precursor. Among
`
`
`
`Lio_95Nio.2sZro.2s Vo.sO2.2, LiCoo.2Nio_3Ago.05 V 0.45O2.1,
`
`
`these, the most preferred method is to use a lithium­
`
`L i C00_4Zro.1 Vo.5O2.0, Li 1.01 C o o,4Lao.1 Vo.sO2.1,
`
`
`
`containing transition metal oxide as the negative electrode
`
`
`
`active material precursor, and to electrochemically insert
`
`
`lithium ions therein. As a method of electrochemically
`
`
`
`
`inserting lithium ions, discharge can be conducted in a
`
`redox system (such as an open system (electrolysis) or a
`
`
`closed system (battery)) having the intended lithium­
`
`
`
`containing transition metal oxide as the positive electrode
`
`
`
`
`
`
`active material (i.e., the negative electrode active material
`
`
`
`precursor of the present invention) and a non-aqueous
`
`
`
`
`electrolyte containing lithium metal or lithium salt as the
`
`
`
`
`
`negative electrode active material. Preferably, lithium ions
`
`RJ Technology Exhibit 2001
`Apple Inc. v. RJ Technology LLC
`IPR2023-01350, Page 6 of 34
`
`

`

`
`
`
`
`Japanese Unexamined Patent Application Publication H7-122298
`
`
`
`
`
`(5)
`
`(0024) Preferred examples of lithium-containing metal
`
`
`
`can be inserted by conducting charging in a redox system
`
`
`
`
`
`
`
`oxide positive electrode active materials in the present
`
`
`(such as an open system (electrolysis) or a closed system
`
`
`
`
`invention include LiyCoO2, LiyNiO2, LiyCoaNi1-aO2,
`
`
`
`(battery)) having lithium-containing transition metal oxide
`
`
`
`LiyCobV1-bOz, LiyCobFe1-bO2, LiyMnzO4, LiyMncC02-
`
`
`
`
`as the positive electrode active material and non-aqueous
`
`
`cO4, LiyMncNiz-cQ4, LiyMncV2-cO4, and LiyMncFe2-cO4,
`
`
`
`
`electrolyte containing lithium salt and negative electrode
`
`
`
`as well as a mixture of LiyMnzQ4 and MnO2, a mixture of
`
`
`
`
`
`active material precursor with a composition different from
`
`
`LizyMnzO3 and MnO2, and a mixture of LiyMn2O4,
`
`
`
`
`that of the positive electrode active material as the negative
`
`
`LizyMn2O3, and MnO2 (where y is within the range of 0.5
`
`
`electrode active material.
`
`
`
`to 1.2, a is within the range of 0.1 to 0.9, b is within the
`(0019) There is no particular restriction on the amount of
`
`
`
`
`range of0.8 to 0.98, c is within the range of 1.6 to 1.96, and
`
`
`
`lithium ions inserted; however, 27 to 1340 mAh per I g of
`
`z is within the range of 2.01 to 5).
`
`
`
`
`
`
`negative electrode active material precursor (equivalent to
`
`
`(0025) More preferred examples of lithium-containing
`
`
`
`1 to 50 mmol) is preferred. 40 to 1070 mAh (equivalent to
`
`
`
`
`metal oxide positive electrode active materials in the
`
`
`1.5 to 40 mmol) is particularly preferred. 54 to 938 mAh
`
`
`
`
`
`present invention include LiyCoO2, LiyNiO2, LiyCoaNi1-
`
`
`(equivalent to 2 to 35 mmol) is most preferred. There is no
`
`
`aO2, LiyCobV1-bOz, LiyCobFe1-bO2, LiyMn2O4,
`
`
`
`particular restriction on the ratio of the aforesaid positive
`
`
`
`LiyMncC02-cO4, LiyMncNi2-cO4, LiyMncV2-cO4, and
`
`
`
`
`electrode active material and negative electrode active
`
`
`LiyMncFe2-cO4 (where y is within the range of 0. 7 to 1.04,
`
`
`
`material that is used; however, it is preferable to set the
`
`
`
`a is within the range of 0.1 to 0.9, b is within the range of
`
`
`
`ratio such that each has a similar effective equivalent (an
`
`0.8 to 0.98, c is within the range of 1.6 to 1.96, and z is
`
`
`
`effective equivalent refers to an equivalent that is
`
`within the range of 2.01 to 2.3).
`
`
`
`substantively able to maintain cyclability). At this time, it is
`(0026) Most preferred examples of the aforesaid lithium­
`
`
`
`
`
`
`also preferred to increase the amount of either the positive
`
`
`
`containing transition metal oxides in the present invention
`
`
`
`
`
`electrode active material or the negative electrode active
`
`
`
`
`include LiyCoO2, LiyNiO2, LiyCoaNi1-aO2, LiyMnzQ4,
`material.
`
`
`and LiyCobV1-bOz (where y is within the range of 0.7 to
`
`
`
`
`(0020) In the present invention, it is preferred that lithium­
`
`
`1.1, a is within the range of 0.1 to 0.9, b is within the range
`
`
`containing transition metal oxide in which the basic crystal
`
`of 0.9 to 0.98, and z is within the range of 2.01 to 2.3).
`
`
`
`structure of the precursor has been altered is used as the
`
`
`
`Furthermore, it is preferred that y is within the range of 0. 7
`
`
`
`
`
`negative electrode active material, and this altered basic
`
`
`to 1.04, a is within the range of 0.1 to 0.9, b is within the
`
`
`
`
`structure is not subsequently altered by charging and
`
`
`range of 0.9 to 0.98, and z is within the range of 2.02 to 2.3.
`
`
`
`discharging. In short, it is preferred that the X-ray
`
`Here, the aforesaid y value is the value prior to starting
`
`
`
`
`diffraction pattern of the negative electrode active material
`
`
`
`charging and discharging, which is increased or decreased
`
`
`
`
`precursor of the present invention is altered by the insertion
`
`by charging and discharging.
`
`
`of lithium ions, but that subsequently it does not
`(0027) Particularly preferred examples of compounds used
`
`
`
`
`
`
`
`
`substantially change even after repeated charging and
`
`
`
`in the present invention will be cited below; however, the
`discharging.
`
`
`
`
`present invention is not exclusive thereto. These examples
`(0021) For the positive electrode active material used in the
`
`
`
`
`
`
`LiCoO2, LiNiO2, LiCoo.sNio.sO2, LiCoo.9sVo.osO2.os,
`include
`
`
`
`
`
`
`present invention, any transition metal oxide capable of
`
`
`
`LiMnO2, and LiMn2O4. Although the positive electrode
`
`
`
`
`releasably storing and releasing lithium ions is acceptable,
`
`
`
`
`active material oxide used in the present invention may be
`
`
`but lithium-containing transition metal oxide is preferred.
`
`
`
`
`either crystalline or non-crystalline, a crystalline compound
`
`
`
`
`Examples of preferred lithium-containing transition metal
`is preferred.
`
`
`
`
`
`oxide positive electrode active materials include lithium­
`(0028) In the present invention, the aforesaid phrase "the
`
`
`
`
`
`
`
`containing oxides that also contain Ti, V, Cr, Mn, Fe, Co,
`
`
`
`
`
`positive electrode active material and the negative electrode
`
`Ni, Cu, Mo, and/or W. It is preferred that the positive
`
`
`
`active material have different compositional formulae"
`
`
`
`
`
`electrode active material and the negative electrode active
`
`signifies that:
`
`
`
`material have different compositional formulae.
`1. The combination of metal elements differs; and
`
`
`
`
`
`(0022) The lithium-containing transition metal oxide
`
`
`
`2.In the case of the example with positive electrode active
`
`
`
`
`
`serving as the positive electrode active material of the
`
`
`
`
`material LiyCobV1-bOz and negative electrode active
`
`
`
`
`present invention is preferably synthesized by mixing a
`
`
`
`material LixCoqV 1-qOj, that y and x, b and q, and z and j
`
`
`lithium compound and one or more types of transition
`
`
`do not simultaneously have the same value. In particular,
`
`metal compounds in such a way that the molar ratio of
`
`this signifies that b and q and z and j do not simultaneously
`
`
`
`lithium compound to total transition metal compound
`have the same value.
`
`
`attains 0.3 to 2.2 (where the transition metal is at least one
`For the positive electrode active material and the negative
`
`
`
`
`
`type selected from Ti, V, Cr, Mn, Fe, Co, Ni, Mo, and W).
`
`
`
`
`
`electrode active material used in the present invention, it is
`
`
`
`Furthermore, it is preferred that the transition metal is at
`
`
`
`preferred to combine compounds that each have a different
`least one type chosen from among V, Cr, Mn, Fe, Co, and
`
`
`standard oxidation-reduction potential.
`Ni.
`
`
`
`
`
`(0029) The positive electrode active material of the present
`(0023) The aforesaid lithium-containing transition metal
`
`
`
`
`
`
`
`oxide serving as the positive electrode active material of
`
`
`
`the present invention can be represented as LiyNOz (where
`
`
`M is a transition metal including at least one type selected
`
`from among Co, Mn, Ni, Vi, and Fe, y is within the range
`
`of 0.3 to 1.2, and z is within the range of 1.4 to 3).
`
`RJ Technology Exhibit 2001
`Apple Inc. v. RJ Technology LLC
`IPR2023-01350, Page 7 of 34
`
`

`

`
`
`
`
`Japanese Unexamined Patent Application Publication H7-122298
`
`
`
`
`(6)
`
`to 1.5 V roughly once every 20 cycles in order to account
`
`
`invention can be produced by chemically inserting lithium
`
`
`
`
`
`
`
`for decrease in battery capacity due to cycling.
`
`ions into a transition metal oxide, by electrochemically
`
`
`
`end voltage to 0.5 V(2)Set the usable range for discharge
`
`
`
`
`inserting lithium ions into a transition metal oxide, or by
`
`or greater and less than 1.5 V. During the aforesaid
`
`
`mixing a lithium compound with a transition metal
`
`
`discharging to 0.5 to 1.5 V, discharging to 0.7 to 1.5 V is
`
`compound and then firing.
`
`
`preferred, and discharging to 0.8 to 1.4 V is particularly
`
`
`
`(0030) When synthesizing the positive electrode active
`
`
`
`preferred. There is a risk of melting the current collector,
`
`
`
`
`material of the present invention, an example of how to
`
`
`etc. if the discharge end voltage is lower than 0.5 V, and
`
`
`
`insert lithium ions into a transition metal oxide is to react
`
`
`
`
`cyclability is impaired if the discharge end voltage is
`
`
`
`
`
`
`either lithium metal, a lithium alloy, or butyl lithium with a
`
`greaterthan 1.5 V, both of which are undesirable.
`
`
`
`
`transition metal oxide. The particularly preferred method of
`
`
`
`
`
`(0034) To ensure that the battery voltage performs up to its
`
`
`
`
`
`synthesizing the positive electrode active material used in
`
`
`
`
`3 V rating, the charge end voltage is preferably within a
`
`
`
`
`the present invention is by mixing a lithium compound with
`
`
`a transition metal compound and then firing.
`
`range of 3.5 to 4.7 V, even more preferably 3.7 to 4.5 V,
`
`
`
`and particularly preferably 3.8 to 4.4 V. Battery voltage
`
`
`
`(0031) The firing temperature of the negative electrode
`
`decreases if this value is less than 3.5 V, and there is risk of
`
`
`
`
`active material and its precursor in the present invention
`
`
`
`breakdown of the positive electrode active material and
`need merely be high enough to be able to break apart and
`
`
`electrolyte if this value is greater than 4.7 V, both of which
`
`
`melt a portion of the mixed compounds used in this
`are undesirable.
`
`
`
`invention; for example, 250 to 2000 °C is preferred, and
`(0035) The negative electrode ac